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1 



IC 


8906 



Bureau of Mines Information Circuiar/1982 



Mineralogical and Elemental Description 
of Pacific Manganese Nodules 



By Benjamin W. Haynes, Stephen L. Law, 
and David C. Barron 




UNITED STATES DEPARTMENT OF THE INTERIOR 



Information Circular 8906 



Mineralogical and Elemental Description 
of Pacific Manganese Nodules 



By Benjamin W. Haynes, Stephen L. Law, 
and David C. Barron 




UNITED STATES DEPARTMENT OF THE INTERIOR 
James G. Watt, Secretary 

BUREAU OF MINES 
Robert C. Norton, Director 



4P 






}^' 



aO- 



As the Nation's principal conservation agency, the Department of the Interior 
has responsibility for most of our nationally owned public lands and natural 
resources. This includes fostering the wisest use of our land and water re- 
sources, protecting our fish and wildlife, preserving the environmental and 
cultural values of our national parks and historical places, and providing for 
the enjoyment of life through outdoor recreation. The Department assesses 
our energy and mineral resources and works to assure that their development is 
in the best interests of all our people. The Department also has a major re- 
sponsibility for American Indian reservation communities and for people who 
live in Island Territories under U.S. administration. 



This publication has been cataloged as follows: 



Haynes, Denjamln W 

Mineralogical and elemental description of Pacific manganese 
nodules. 

(Information circular/ Bureau of Mines ; 8906) 

Supt.ofDocs.no.: 128.27:8906. 

1. Manganese nodules— Pacific Ocean. 1. Law, Stephen L. II. 
Barron, D. C. (David C). III. Title. IV. Series: Information circu- 
lar (United States. Bureau of Mines) ; 8906. 



TN2957tM- [QE390.2.1V135] 622s [549'. 23] 82-600495 



For sale by the Superintendent of Documents, li.S. Government Printing Office 

Washington, B.C. 20402 



J 






CONTENTS 



QQ. 



Page 



Abstract 1 

Introduction 2 

Acknowledgments 3 

Manganese nodules 3 

Morphology 3 

Mineralogy 10 

Manganese minerals 11 

Todorokite or 1 A manganite 11 

Birnessite or 7 A manganite 12 

Vernadite or 8-Mn02 12 

Other manganese minerals 13 

Manganese mineral-element associations 13 

Iron oxide minerals 13 

Feroxyhyte 14 

Goethite 14 

Lepidocrocite 14 

Other iron oxide minerals 14 

Iron oxide mineral-element association 14 

Accessory minerals 14 

Sheet silicates and zeolites 14 

Clastic silicates and volcanics 15 

Biogenics 15 

Sea salt residue 15 

Accessory mineral-element associations 17 

Moisture content 17 

Elemental composition 17 

Major and minor elements of potential 

economic interest 17 

Manganese 17 

Iron 18 

Nickel 18 

Copper 18 

Cobalt 23 

Zinc 23 



Page 

Vanadium ?3 

Molybdenum 23 

General observations 28 

Other major and minor elements 28 

Aluminum 28 

Calcium 30 

Magnesium 30 

Potassium 30 

Silicon 30 

Sodium 30 

Strontium 31 

Titanium 37 

Zirconium 37 

General observations 37 

Elements of environmental interest 37 

Arsenic 37 

Barium 40 

Cadmium 40 

Chromium 40 

Lead 40 

Mercury 45 

Selenium 45 

Silver 45 

General observations 45 

Rare-earth elements 46 

Precious-metal-group elements 49 

Radioactive elements 49 

Other trace elements 50 

Anion-forming elements 51 

Summary tables 52 

Cross section analysis 52 

References 57 

Appendix. — Glossary of mineralogical terms 60 



ILLUSTRATIONS 



1 . Map of the Pacific Ocean showing CC Zone and MPS areas 2 

2. Northern Pacific spheroidal nodules with smooth surface texture 4 

3. Study collection of manganese nodules from R/V Prospector 5 

4. Discoidal nodules from box cores 6 

5. Ellipsoidal nodule with large botryoidal surface protrusions and coarse granular surface texture 7 

6. Flat-faced or angular nodules with relatively smooth surface texture 7 

7. Cross section of ellipsoidal Pacific nodule 8 

8. Cross section of north Pacific nodule 9 

9. Contrasting surface textures, smooth and granular, on opposing sides of three nodules 10 

10. Irregular layering with maximum thickness toward bottom of north Pacific nodule 10 

1 1 . Electron microscope observation of todorokite 12 

12. Proposed atomic arrangement for one common todorokite structure 13 

13. Scanning electron photomicrograph showing crystals of the zeolite phillipsite in an oxide 

cavity of a manganese nodule 16 

14. Manganese frequency distribution by environment for Pacific manganese nodules 19 

1 5. Iron frequency distribution by environment for Pacific manganese nodules 20 

16. Nickel frequency distribution by environment for Pacific manganese nodules 21 

17. Copper frequency distribution by environment for Pacific manganese nodules 22 

18. Cobalt frequency distribution by environment for Pacific manganese nodules 24 

19. Zinc frequency distribution by environment for Pacific manganese nodules 25 

20. Vanadium frequency distribution by environment for Pacific manganese nodules 26 

21 . Molybdenum frequency distribution by environment for Pacific manganese nodules 27 

22. Aluminum frequency distribution by environment for Pacific manganese nodules 29 

23. Calcium frequency distribution by environment for Pacific manganese nodules 31 

24. Magnesium frequency distribution by environment for Pacific manganese nodules 32 

25. Potassium frequency distribution by environment for Pacific manganese nodules 33 

26. Silicon frequency distribution by environment for Pacific manganese nodules 34 

27. Sodium frequency distribution by environment for Pacific manganese nodules 35 



\-' 



IV 

Page 

28. Strontium frequency distribution by environment for Pacific manganese nodules 36 

29. Titanium frequency distribution by environment for Pacific manganese nodules 38 

30. Zirconium frequency distribution by environment for Pacific manganese nodules 39 

31 . Arsenic frequency distribution for Pacific manganese nodules 40 

32. Barium frequency distribution by environment for Pacific manganese nodules 41 

33. Cadmium frequency distribution by environment for Pacific manganese nodules 42 

34. Chromium frequency distribution by environment for Pacific manganese nodules 43 

35. Lead frequency distribution by environment for Pacific manganese nodules 44 

36. Mercury frequency distribution for Pacific manganese nodules 45 

37. Selenium frequency distribution for Pacific manganese nodules 45 

38. Silver frequency distribution for Pacific manganese nodules 45 

39. Lanthanum frequency distribution for Pacific manganese nodules 46 

40. Cerium frequency distribution for Pacific manganese nodules 46 

41 . Neodymium frequency distribution for Pacific manganese nodules 46 

42. Samarium frequency distribution for Pacific manganese nodules 46 

43. Europium frequency distribution for Pacific manganese nodules 47 

44. Gadolinium frequency distribution for Pacific manganese nodules 47 

45. Terbium frequency distribution for Pacific manganese nodules 47 

46. Holmium frequency distribution for Pacific manganese nodules 47 

47. Thulium frequency distribution for Pacific manganese nodules 48 

48. Ytterbium frequency distribution for Pacific manganese nodules 48 

49. Lutetium frequency distribution for Pacific manganese nodules 48 

50. Hafnium frequency distribution for Pacific manganese nodules 48 

51 . Thorium frequency distribution for Pacific manganese nodules 49 

52. Uranium frequency distribution for Pacific manganese nodules 49 

53. Antimony frequency distribution for Pacific manganese nodules 50 

54. Boron frequency distribution for Pacific manganese nodules 50 

55. Niobium frequency distribution for Pacific manganese nodules 50 

56. Rubidium frequency distribution for Pacific manganese nodules 51 

57. Scandium frequency distribution for Pacific manganese nodules 51 

58. Thallium frequency distribution for Pacific manganese nodules 51 

59. Tin frequency distribution for Pacific manganese nodules 51 

60. Yttrium frequency distribution for Pacific manganese nodules 51 

61 . Unpolished cross section of nodule DH 9-9 55 

62. Spatial distribution of nickel and copper concentrations with respect to discrete sample locations on nodule 

DH 9-9 cross section 56 

63. Spatial distribution of cobalt and zinc concentrations with respect to discrete sample locations on 

nodule DH 9-9 cross section 56 

64. Spatial distribution of iron and lead concentrations with respect to discrete sample locations on 

nodule DH 9-9 cross section 56 

65. Spatial distribution of barium and cerium concentrations with respect to discrete 

sample locations on nodule DH 9-9 cross section 56 



TABLES 

1 . Morphological characteristics of Pacific manganese nodules 4 

2. Manganese minerals in Pacific manganese nodules 11 

3. Iron oxide minerals in Pacific manganese nodules 13 

4. Accessory minerals in Pacific manganese nodules 15 

5. Distribution of elements of potential economic interest in Pacific manganese nodules, by area 18 

6. Distribution of elements of potential economic interest in Pacific manganese nodules, composite 18 

7. Distribution of other major and minor elements in Pacific manganese nodules, by area 28 

8. Distribution of other major and minor elements in Pacific manganese nodules, composite 28 

9. Distribution of elements of environmental interest in Pacific manganese nodules, by area 37 

10. Distribution of elements of environmental interest in Pacific manganese nodules, composite 40 

1 1 . Rare-earth elements in Pacific manganese nodules 47 

12. Precious-metal-group elements in Pacific manganese nodules 49 

13. Radioactive elements in Pacific manganese nodules 49 

14. Other trace elements in Pacific manganese nodules 50 

1 5. Anion-forming elements in Pacific manganese nodules 52 

16. Summary of major, minor, and some trace elements in Pacific manganese nodules, by area 52 

1 7. Summary of elements in Pacific manganese nodules 53 

18. Elements for which no data were found for Pacific manganese nodules 53 

19. Interelement correlation coefficients for Pacific manganese nodules, by area 53 

20. Nodule cross section sample locations and analysis 55 



LIST OF UNIT OF MEASURE ABBREVIATIONS USED IN THIS REPORT 



A 


angstrom 


atm 


atmosphere 


cm 


centimeter 


"C 


degrees Celsius 


m 


meter 


mm 


millimeter 


p.m 


micrometer 



ng/g 


nanograms per gram 


pet 


percent 


pg/g 


picograms per gram 


ppm 


parts per million 


wt-pct 


weight-percent 


yr 


year 



MINERALOGICAL AND ELEMENTAL DESCRIPTION 
OF PACIFIC MANGANESE NODULES 



By Benjamin W. Haynes,' Stephen L. Law,^ and David C. Barron' 



ABSTRACT 



This Bureau of Mines publication comprises a compilation of the state of the science in 
Pacific Ocean manganese nodule mineralogy and elemental composition. The report is 
divided into three sections: morphology, mineralogy and elemental composition. 

The nodule morphology section defines what is considered a nodule for the study, and 
details the external characteristics and internal structure. Nodule mineralogy is discussed 
in three sections: manganese minerals, iron oxide minerals, and accessory minerals. The 
major manganese minerals discussed are todorokite, birnessite, and vernadite. The iron 
oxide minerals are less well known and include feroxyhyte, goethite, and lepidocrocite. 
Accessory minerals present include quartz, clays, and other silicates and nonsilicates. A 
discussion on moisture content is also included. 

The elemental composition section presents data on 74 elements occurring as cations or 
anions. Summary data, histograms, and interelement correlation coefficients are 
presented. The elements are grouped as follows: major and minor elements of potential 
economic interest (8), other major and minor elements (9), elements of environmental 
interest (8), rare-earth elements (15), precious-metal-group elements (6), radioactive 
elements (3), other trace elements (17), and anion-forming elements (8). Cross sectional 
determinations of Ni, Cu, Zn, Co, Pb, Fe, Ce, and Ba are given for a single nodule to show 
the general tendency of different growth patterns within a nodule because of different 
element associations and composition. 

' Supervisory research chemist, Avondale Research Center, Bureau of Mines, Avondale, Md. 
^ Research supervisor, Avondale Research Center, Bureau of Mines, Avondale, Md. 
^ Chemist, Avondale Research Center, Bureau of Mines, Avondale, Md. 



INTRODUCTION 



This report is one in a series of reports to be issued by the 
Bureau of IVIines to document the results of a project entitled 
"Analysis and Characterization of Manganese Nodule 
Processing Rejects." Deep seabed mining for manganese 
nodules, including the processing of nodules to recover value 
metals, raises a variety of environmental, social, and 
economic considerations. To address the waste manage- 
ment aspects of the recovery of value metals from nodules, 
the National Oceanic and Atmospheric Administration 
(NOAA) of the Department of Commerce, the Environmental 
Protection Agency, and the Department of the Interior's 
Bureau of Mines and Fish and Wildlife Service, after 
consultation with affected and concerned interests, have 
agreed to embark on a mulfiyear cooperative research 
program that has the following overall objective: 

'To provide information needed by Federal and State 
agencies in preparation for receipt of industry's commer- 
cial waste management plans." 

The NOAA-funded research being conducted by the 
Bureau of Mines has the objective of obtaining a "first-order 
chemical and physical characterization of rejects from the 
types of manganese nodule processing techniques repre- 
sentative of those being developed by industry." To better 
understand the nature of the waste rejects coming from 
nodule processing, data were first obtained on the mineralog- 
ical and chemical composition of manganese nodules from 
throughout the Pacific Ocean, as outlined in this report. After 
characterization of the nodule feed material, the major 
proposed processing schemes are being operated on a 
bench scale to generate rejects for study. These labora- 
tory-generated rejects will be compared with industry pilot 
plant-generated rejects as they become available from the 
various deep ocean mining consortia. 

The data from this research will be published for use by (a) 
industry and environmental scientists in subsequent re- 
search to assess the potential effects of waste management 
alternatives; and (b) regulatory agencies in the determination 
of standards and test requirements to be met. This is 
expected to facilitate the development of a basic framework 
that accommodates the desire to assure protection of the 
environment and the development of a new minerals 
processing industry. 

In order to assess the potential effects of disposing of 
reject waste materials from manganese nodule processing, 
the elemental composition, the compounds present, the 
interelement correlations, and the mineralogical structure of 
manganese nodules must be determined. Because nodules 
from the Pacific Ocean have higher Cu, Co, and Ni contents 
than nodules from other areas, this report will focus on the 
Pacific Ocean manganese nodules 'vith an emphasis on the 
area between the Clarion and Clipporton Fracture Zones (CC 
Zone) in the equatorial northeast Pacific (fig. 1). Major 
consortia involved at this time in deep ocean mining and 
processing of nodules have extensively surveyed the CC 
Zone area in the Pacific Ocean. Under the Deep Seabed 
Hard Minerals Resources Act of 1980 (PL 96-283), NO.AA 
has been designated as the lead agency in developing terms, 
conditions, and restrictions for the proposed mining of 
nodules and the disposal of waste generated. 

This report, focusing on the elemental and mineralogical 
composition of Pacific Ocean manganese nodules, is divided 
into the following three sections: 

1 . A description of manganese nodules as they occur in 
the Pacific Ocean. 

2. Mineralogical composition and element-mineral asso- 
ciations. 

3. Elemental composition and interelement correlations. 




Figure 1 . — Map of the Pacific Ocean showing CC 
Zone and IMPS areas. 



The elemental composition is presented for major and 
some minor and trace elements by areas of the Pacific in the 
form of histograms. These areas are as follows: 

1 . The Clarion-Clipperton Fracture Zone area. 

2. The mid-Pacific seamounts area (MPS), <3,000-m 
depth. 

3. Other abyssal plains area (>3,000-m depth and 
exclusive of CC Zone). 

4. Other seamounts, ridges, and continental margins area 
(<3,000-m depth). 

The elements for which data were insufficient to be 
presented by area, are presented as a composite of the 
Pacific Ocean nodule population. The majority of data for all 
elements, however, is from the CC Zone owing to 
commercial interest, abundance, and grade of deposits 
found there. No data are presented for Indian and Atlantic 
Ocean nodules. Figure 1 shows the CC Zone and MPS areas 
of study used in this report. The other two areas comprise the 
remainder of the Pacific Ocean. 

The mineralogical composition of nodules is presented for 
the entire Pacific Ocean with some emphasis placed on 
major mineral differences with respect to environment 
(depth, sediment type, etc.). The interelement correlations 
are presented for the major, some minor, and some trace 
elements where a significant positive or negative correlation 
was determined. The element-mineral associations are 
presented for those elements where the evidence is 
supportive. 

Information and data contained in this report were obtained 
through many sources. The majority of the elemental and 
mineralogical information came from the following sources: 
The Sediment Data Bank, operated by Science Applications, 
Inc., (SAI) in LaJolla, Calif.; the Bureau of Mines nodule data 
base at the Denver (Colo.) Research Center; Bureau of 
Mines in-house research; published literature; other gov- 
ernmental agencies; private industry and consulting firms; 
and personal contacts with experts in the field of nodule 



chemistry and mineralogy {1-2, 9-10, 12-13, 25-26, 31, 
38-39, 41-45, 47-50, 60, 63, 67-68, 72, 74, 79-89, 91, 93, 
95-97, 102, 107, 109-110, 112-114, 118, 121-128, 130-132).' 
Special mention should be made of the extensive reliance 
upon the books, Marine Manganese Deposits, edited by G. 



P. Glasby (59); Manganese Nodules, by R. K. Sorem and R. 
H. Fewkes (117); and Marine Minerals (17), edited by R. G. 
Burns, for information on the description and mineralogy of 
Pacific manganese nodules. 



ACKNOWLEDGMENTS 



This work was performed under interagency agreement 
NA80AAGO 3026 with the Department of Commerce, 
National Oceanic and Atmospheric Administration (NOAA). 
The overall research direction and monitoring responsibilities 
of Amor L. Lane, M. Karl Jugel, and Robert F. Dill, Office of 
Oceanic fvlinerals and Energy, NOAA, and of Thomas A. 
Henrie, Chief Scientist, Bureau of Mines, are gratefully 
acknowledged. 

The authors wish to thank Virginia M. Burns and Roger G. 
Burns, Massachusetts Institute of Technology, Cambridge, 
Mass., for their many helpful discussions, comments, and 
reviews as well as their assistance in providing information 



on newly published articles and also for their assistance in 
providing scanning electron microscope photomicrographs of 
nodules. The authors also thank Ronald K. Sorem, 
Washington State University, Pullman, Wash., for assistance 
in providing nodule photographs, Ronald H. Fewkes, 
consultant, Pullman Wash., for manuscript review, Jane B. 
Frazer, Chevron Research Co., Richmond, Calif., for 
providing the required information from the Sediment Data 
Bank, and Allan R. Foster, NORTECH, Kirkland, Wash., and 
Mike Williamson, consultant, Kirkland, Wash., in providing 
the cross-sectional analysis. 



MANGANESE NODULES 



Ferromanganese oxides are deposited in a variety of forms 
in marine environments. In reporting on samples collected by 
the H.M.S. Challenger expedition (1872-76), Murray and 
Renard (101) noted hydrates of manganese as "colouring 
matters, or as thin or thick coatings on shells, corals, shark's 
teeth, bones, and fragments of rock." There is no universally 
accepted delineation between objects that are stained or 
very thinly encrusted with manganese and objects that may 
be called manganese nodules (59). However, for purposes of 
chemical comparison of nodules from throughout the Pacific 
Ocean, a "manganese nodule" will be arbitrarily defined as 
having a ferromanganese oxide encrustation at least four 
times greater in bulk than the nucleus object. Otherwise, a 
nucleus, or multinucleated objects, greater than 20 pet of the 
total weight will have too significant an influence upon the 
observed chemistry of the specimen for valid comparisons 
with manganese nodules having small nuclei. For example, 
the Drake Passage series of nodules described by Sorem 
and Fewkes (117) contain rock fragment cores comprising 
50 pet or greater of the nodule and are therefore not included 
in the study. Also, it is doubtful that thinly encrusted objects 
will ever be considered commercially attractive in the same 
sense as implied in the term "manganese nodule." Of course, 
if the nucleus of a nodule is a fragment of another nodule, it 
will be classified as a manganese nodule regardless of 
nucleus size. 

Manganese micronodules are a special case of the nodule 
category not included in this study. Micronodules are 
individual grains generally less than 1 mm in diameter and 
usually lack a discernible nucleus. Also not included as 
manganese nodules are the large, slablike concretions such 
as the manganese pavement from the San Pablo Seamount 
described by Aumento (6). 



The existence of varying populations of nodules at different 
localities in the Pacific Ocean can be attributed to several 
factors including type of nucleation substrate available, 
bathymetric position, bottom current activity, sediment type, 
benthic organism activity, and the chemical environment 
(59). Details of nodule genesis are still poorly understood, 
though the layering nature and chemical associations 
characteristic of manganese nodules have been known for 
many years. 

That nodule formation requires some special conditions is 
illustrated by the discontinuous distribution of nodule fields 
and the fact that some fields are rich in Mn, Cu, and Ni 
whereas others, with essentially the same underlying 
sediments, are high in Fe and low in Mn, Cu, and Ni. Nodules 
apparently accrete from both sides, with nickel and copper 
accreting primarily from the sediment side. Raab and Meylan 
(59, pp. 109-146) were unable to verify that chemical 
gradients found in nodules could be ascribed to the upward 
migration of trace metals owing to diffusion, and their theory 
on accretion only on the sediment side is no longer accepted 
by most researchers. Intraplate igneous activity resulting in 
the extraction and transport of metals from the sediment to 
the mud-water interface is postulated by Raab and Meylan 
(59, pp. 109-146) as the source of metals for the concentric 
layering of nodules. Once the warm, metal-rich brine layer is 
dissipated, the newly formed nodules are exposed to normal 
seawater leaching of metals until the next intraplate intrusive 
event. 

The key to a more complete understanding ot manganese 
nodule origin lies in the domain of researchers studying the 
microfeatures and chemical associations in nodules from 
many areas and is beyond the scope of this report. 



MORPHOLOGY 



Table 1 provides an abbreviated summary of the nature 
and variability of the morphological characteristics of Pacific 

■* Italicized numbers in parentheses refer to items in the list of references 
preceding the appendix. 



manganese nodules. The term morphology is used here in its 
broadest sense to include not only external shape but also 
the internal structure of the nodule contributing to the total 
nodule properties. 
Figures 2 through 6 show examples of five external 



Table 1 Morphological characteristics of Pacific manganese nodules 

Characteristic Nature and extent of variability 

Size Generally 0.5 to 20 cm. Concretions larger than about 20 cm in diameter generally assume the form of slabs. 

External shape Numerous terms used. Most frequent are — 

Spheroidal (peas to cannonballs). 

Ellipsoidal (potatoes). 

Discoidal or tabular (includes slabs). 

Botryoidal, poiylobate, or coalespheroidal (grape cluster). 

Flat faced or polygonal (or irregular shape, owing to angular nucleus or fracturing). 

Surface texture Surfaces are usually mammillated, with texture occurring in two general classifications — 

Smooth: Smooth to the touch and to the eye, though close examination may reveal densely packed minute botryoids. 
Granular; Feels gritty and may leave tiny oxide particles on the hand upon handling. Close examination may show tiny, 

closely spaced dendritic oxide forms that may be so abundant in some nodules that the surface botryoids are almost 

completely obscured. 

Color Refers to nodule exterior, free of clay. Generally dark reddish brown to black, with variations of black as the most common 

color. 

Crustal zone The outermost layer or set of layers that appear to represent continuous accretion up to the time of collection. Varies from 

well-defined, uniform to asymmetric, to very thin or absent. 

Nucleus Can be any solid object. Often influences external shape of nodule. Examples — 

Rock: Igneous, metamorphic, sedimentary. 
Nodule fragment. 
Slab of clay. 

Biological fragment: Tooth, vertebra, bone, fossil, sponges, etc. 
Volcanic glasses — like pumice, glassy lapilli — almost always profoundly altered. 

No apparent foreign nucleus: fvlay have formed around a nodule fragment with indeterminate laminations, or original 
nucleus was altered and replaced. 

Internal fractures Generally filled with clay and readily visible in cut nodules. Occasional clay-free fractures lined with overgrowth of 

ferromanganese oxides. Two types — 
Radial or random: An extension feature having greatest separation toward center of nodule and tapering toward edges. 

Often do not emerge at surfaces but some open toward the sediment side. Show characteristics of shrinkage cracks. 
Concentric: A fracture along nodule zoning but almost never continuous around entire nodule, frequently terminated by 
radial fractures. 

Breaks Breakup generally attributed to benthic organisms or bottom currents acting on a fracture-weakened nodule. Terms 

include — 
Spalling: Peeling of layers, obsen/ed occasionally only in larger nodules (7-cm diam. or larger). 
Cross section: Transects the nodule layers more or less at right angles; a more common break, 
a-breaks: Fresh breaks essentially complete before physical recovery from the ocean floor, with the final break 

occurring during handling in a crust holding the nodule together; more common in larger nodules, 
p-breaks: Old fracture surfaces with entire fracture covered by a crust of manganese material; more common in smaller 
nodules (<7-cm diam.). 

Interior zoning Some zonal pattern in nodule cross section, produced by variation in mineral content of the growth layers, is generally 

present in all nodules. Three types — 
Continuous, varied bands: Thicker in one half of the nodule, tapering to a thin portion starting near the equator and 
becoming very thin at the side opposite the thick portion. Textures and composition of the two portions of tfie band 
usually differ. 
Continuous, uniform bands: Often close to the core, suggesting a uniform growth environment. 
Discontinuous bands: Bands that are completely terminated, usually by sudden tapering near the nodule equator. 





1 
Scale, cm 

Figure 2. — Northern Pacific spheroidal nodules 
with smooth surface texture. Latitude 32° 43' N, 
longitude 158° 15.8 W; depth dredged, 1,120 to 

1 ,400 m. Photograph courtesy of reference 1 17, p. 37. 




Scale, cm 



reference 10, p. 493. 









Figure 4. — Discoidal nodules from box cores. Side views (a, d); top views (b, e); bottom views (c, f). 
Botii nodules are from DOMES RP8-OC-76, leg 9. Top nodule is from 151 1.73 N. latitude, 126°03.89 W. 
longitude at a depth of 4,524 m. Bottom nodule is from 1 5°1 3.04 N. latitude, 1 25°55.94' W. longitude at a 

depth of 4,465 m. Photograph courtesy of reference 1 1 7, p. 39. 



shapes, listed in table 1 , generally exhibited by Pacific 
manganese nodules — spheroidal, ellipsoidal, discoidal, bot- 
ryoidal, and flat faced. The shape of a nodule, especially the 
smaller flat faced nodules, may be influenced by the shape of 
the nucleus. Table 1 lists the various solid objects that may 
form the nucleus, and figures 7 and 8 show examples of 
nuclei. These photographs were taken in reflected light with 
vertical illumination so that oxides appear bright and clay 
materials appear dark. 

Figure 9 shows the two general surface textures, smooth 
or granular, in this case occurring on opposite sides of the 
same nodules. A different surface texture for the top and 
bottom of a nodule is not uncommon, especially for the larger 
asymmetric nodules. 

Nodule size is an important factor because of the 
relationship between mineralogy and the nodule contact with 
ocean floor sediments. Accretion of crystalline manganese 
oxides seems to be enhanced on the portion of the nodule 
resting in water-saturated, fine-grained silicate sediments. 
Small nodules (<3-cm diam.), virtually enclosed in soupy 
sediment, tend to accrete crystalline oxides on all sides and 
maintain a spheroidal or ellipsoidal shape, or maintain the 
shape of the nucleus. At a size of about 3 cm or greater, 
nodules usually tend to develop a pronounced asymmetry of 
shape because of nonuniform growth rates. The most 
common pattern is a gradual increase in the horizontal 
dimensions so that a spheroidal nodule becomes ellipsoidal, 
and an ellipsoidal nodule approaches a discoidal shape. 
When the top of the larger nodule comes in contact with 
relatively sediment-free water, thin iron-rich amorphous 
oxide layers are slowly added. The bottom and sides of the 
large nodule, however, remain in contact with watery 
sediment and continue adding layers of crystalline manga- 
nese oxides in which fine silicate grains from the substrate 
are entrapped. 



The accentuated asymmetrical shape of many nodules is 
due to the more rapid deposition of manganese-rich oxides 
compared with the amorphous iron-oxide layer growth, and 
growth of the manganese-rich layers is further enhanced by 
the incorporation of sediment. The cross-sectional zonal 
patterns, shown in figure 1 and summarized in table 1 , show 
the two principal types of growth passing gradationally from 
one to the other near the equator of the nodule. The 
photograph in figure 10 was taken in reflected light with 
vertical illumination so that oxides appear bright and clay 
materials appear dark. 

The upper surface and the bottom surface of a nodule are 
usually chemically different from each other and from the 
nodule interior. The top is generally high in Fe, Co, and Pb 
and low in Cu, Ni, Mo, Zn, and Mn; the bottom shows the 
reverse general pattern. The equatorial area of the surface 
shows intermediate concentrations of the metals. The core of 
a nodule is often deficient in Fe, Co, and Pb content relative 
to the crustal surface. However, the zoning within a nodule 
generally exhibits the same antithetic relationship between 
manganese content and iron content, and provides further 
evidence for the different growth process for the top and 
bottom portions of nodules. This gradational variation in the 
character, of a layer is called a fades change. The texture of 
the layer refers to the relationships of the intergrown oxides 
and nonoxides. The variations in texture are often accompa- 
nied by variations in thickness of layers. 

With aging, only limited changes seem to occur in the older 
layers of a nodule. These include the development of 
shrinkage cracks, both radial and concentric, followed by 
deposition of oxide veinlets and clay fillings from solutions 
circulating along the cracks and through pore spaces. The 
nodule cracking and subsequent physical disturbance may 
result in breakage of the nodule. As noted in table 1, older 
fracture surfaces with the entire fracture covered by an oxide 




Scale, cm 



Figure 5. — Ellipsoidal nodule with large bot- 
ryoidal surface protrusions and coarse granular 
surface texture. Southern Pacific Ocean, latitude 

1 5° S., longitude 90° W. Photograph courtesy of reference 
117, p. 41. 





Scale, cm 



Figure 6 — Flat-faced or angular nodules with relatively smooth surface texture. Minute botryoids 
cover left nodule. Botryoids are much larger on the right nodule. Pacific Ocean locations: left, latitude 

15° S., longitude 145° W.; right, latitude 10° S., longitude 150° W. Photograph courtesy of reference 117, p. 41. 




*^^ 



Scale, cm 



Figure 7. — Cross section of an ellipsoidal Pacific nodule, latitude 9°59.3' N., longitude 152°56.7' W., 
from a depth of about 5,000 m, showing a multiple nuclei core: two subround clay fragments, one shark 
tooth, and one bone fragment. The original nodule enclosed these fragments, was broken, and a 

fragment formed the core of the final nodule. Photograph courtesy of reference 117, p. 253. 




Scale, cm 



Figure 8 Nodule cross section of a north Pacific specimen, latitude 11°21.4' N., longitude 153°37.5' 

W., from a depth of 5,190 m, showing the angular fragment of another nodule as the nucleus. Photograph 

courtesy of reference 117, p. 251. 



10 





Figure 9 Contrasting surface textures, smooth 

and granular, on opposing sides of tliree nodules 
(a-d, b-c and c-f) from latitude 10° N., longitude 140° 
W., at a depth of about 4,500 m. The large nodule is 

approximately 9 cm long. Photograph courtesy of 
reference 1 1 7, p. 43. 



crust are referred to as p-breaks. Fractures that occur at the 
time of nodule removal from the ocean floor environment are 
called a-breaks. 



Scale, cm 



Figure 10. — Irregular layering with ^.he maximum 
thickness toward the bottom of a north Pacific 
nodule from latitude 14°35 N., longitude 124°26' 

W., at a depth of about 4,353 m. Photograph courtesy of 
reference 1 1 7, p. 523. 



Recrystallization and/or replacement of oxides and nonox- 
ides may be observed to some extent in older nodules, and 
alteration or even complete replacement of the original 
nucleus may occur. Basically, however, the mineralogy and 
most of the textural features in nodule interiors are virtually 
identical to the outermost layers, indicating that most nodules 
change little upon aging. 



MINERALOGY 



Manganese nodules consist of a complex mixture of 
materials, including organic and colloidal matter and nucleus 
fragments as well as crystallites of various minerals of detrital 
and authigenic origins. The phases in nodules are fine 
grained, often metastable, poorly crystallized, and so 
intimately intergrown that it is often quite difficult to 
characterize the minute mineral crystallites or to extract a 
homogeneous, single-phase mineral sample for study. The 
minerals are usually characterized by numerous structural 



defects, essential vacancies that may not be ordered, 
domain intergrowths, extensive solid solution, and cation 
exchange properties that lead to nonstoichiometry and 
detract from long-range ordering of the crystals. Distin- 
guishing between authigenic and detrital minerals, particular- 
ly the silica, clay, and iron oxyhydroxide phases, is also a 
challenge, as these phases either formed in situ or were 
transported to the nodule as suspensions in seawater. 
The major interest in manganese nodules centers on the 



11 



oxide minerals of manganese and iron. However, mention 
will also be made of authigenic and detritai accessory 
phases. For the purposes of this study, a mineral is defined 
as an inorganic solid with a crystalline particle size exceeding 
30 to 40 A, having a limited chemical composition range and 
a systematic three-dimensional atomic order. The isotropic 
oxides in manganese nodules are amorphous to X-ray 
diffraction and cannot be classified usefully by optical means. 
Particle sizes less than 30 to 40 A are also amorphous even 
to electron microscopy. These amorphous materials in 
manganese nodules and other materials lacking an internal 
structure of atoms are not included as minerals, but are 
classed as mineraloids. 

Prior to discussion ot the manganese, iron, and accessory 
mineral phases, it is important to note that much of the work 
involving the minerals present in manganese nodules is 
based on laboratory studies using special sampling tech- 
niques, especially in the case of the iron phase. Standard 
X-ray diffraction techniques cannot generally determine more 
than one or two of the manganese and accessory phase 
minerals. The best results to date have been obtained by 
scanning and transmission microscope studies. Recent work 
by Turner (124-126) and Siegel [113) has determined the 
existence and structure of todorokite in manganese nodules. 
Chukhrov (34-36) has done research on the iron phases in 
nodules, but identification is difficult because of the need to 
preserve the nodule mineralogy once the nodule is removed 
from the ocean and the potential for dehydration and 
oxidation of both the manganese and iron phase minerals. 



MANGANESE MINERALS 

Manganese forms a large number of oxide minerals, but 
only the low-temperature oxides that can be formed in water 
are relevant to the mineralogy of nodules. The tetravalent 
manganese predominates in nodules, but the presence of 
Mn^" and Mn^* ions in some phases has been inferred from 
crystallographic and thermodynamic data. Table 2 lists the 
oxide phases of manganese relevant to manganese nodule 
mineralogy as provided by Burns and Burns (59, pp. 
185-248). Available crystallographic data, crystal structures, 
chemical composition, and references to occurrence in 
nodules are also provided. The mineral listing in table 2 
follows an approximate order of increasing complexity of 
crystal structure and decreasing oxidation state of the 
manganese. 



Todorokite, birnessite, and vernadite are the predominant 
manganese oxide minerals, occurring as cryptocrystalline 
phases in manganese nodules. The todorokite and birnessite 
appear to contain variable linkages of edge-shared [MnOe] 
octahedra and are characterized by numerous structural 
defects, cation vacancies in the chains or layers of linked 
octahedra, domain intergrowths of mixed periodicities, cation 
exchange properties, and extensive substitution of Ni^, 
Cu^% Zn^\ Mg^*, or other divalent ions for Mn^". The 
formation of vernadite, sometimes catalyzed by microorga- 
nisms, results in a poorly crystalline to amorphous phase with 
high surface area and cation adsorption properties, concen- 
trating cobalt by substitution of Co^' for Mn^' (13, 100). 
Postdepositional rpcrystallization of vernadite to todorokite 
may occur inside manganese nodules. 

Todorokite or 10-A Manganite 

The manganese oxide mineral characterized by X-ray 
diffraction lines at 9.5 to 9.8 A and 4.8 to 4.9 A is one of the 
most common phases observed in manganese nodules. This 
phase, a hydrated Mn-Mg-Ca-Na-Ni-Cu oxide often with 
significant concentrations of nickel and copper, has been 
identified as either todorokite or 10-A manganite. A synthetic 
structural analog of todorokite also gives a -10- A diffraction 
peak, but to avoid confusion with the mineral manganite 
(7-Mn"'00H), this synthetic 10-A manganite phase, called 
buserite in honor of W. Buser (73), is generally considered 
not to occur in nodules. 

The chemical formula for todorokite is 
(Mn^*,Ca,Mg)Mn3''-07-H20 (46). The marine form of todoro- 
kite found in manganese nodules as adopted by Burns and 
Burns (17) is (Ca,Na,K)(Mg, Mn^jMns^ Oig-HjO. Most 
todorokites consist of fibrous aggregates of small acicular 
crystals. The crystals consist of narrow laths or blades 
elongated along the b axis (fig. 11) and frequently show two 
perfect cleavages parallel to the (001) and (100) planes. 
These fibers are commonly twinned at 120° angles. 
Chukhrov (31-33) has indicated that as many as five 
todorokite polymorphs might exist, all having similar b (2.84 
A) and c (9.59 A) unit cell parameters, but with the a 
parameters as multiples of 4.88 A. 

Todorokite, both terrestrial and marine, has a tunnel 
structure with single, double, and triple chains of edge- 
shared [MnOg] octahedra (31-33, 124-126) along the b axis. 
Essential Mn^* and other divalent cations of comparable ionic 
radii (e.g., f^g^^ Co^\ Ni^*, Cu^*, Zn^) may be located in 



Table 2. — Manganese minerals In Pacific manganese nodules 



Mineral 



Approximate formula 



Crystal system and Cell parameters. A 

space group a b c 

Tetragonal. PAs/mnm 4 39 4.39 2.87 

Orthorhombic, Pbnm 4.53 9.27 2.87 

Hexagonal, NA 9.65 NAp 4.43 

(Tetragonal, 14/m 9.96 9.96 2.86 

iMonoclinic, P2,/n 10.03 5.76 9.90 

/Tetragonal, 14/m 9.84 9.84 2.86 

IMonoclinic, 12/m 9.79 2.88 9.94 

fMonoclinic, A2/m 9.56 2.88 13.85 

lOrthorhombic, P2,2,2 8.254 1 3 40 2.864 

Monoclinic, NA 9.75 2.85 9.59 

Hexagonal^ NA 8.41 NAp 10.01 

Triclinia, PI 7.54 7.54 8.22 

Orthorhombic, NA 8.54 15.39 14.26 

Hexagonal, NA 2.84 NAp 7.27 

Hexagonal, NA 2 85 NAp 7.08- 

7.31 

Hexagonal, NA 2.86 NAp 4.7 

Hexagonal 2.84 NAp 7 07 

Orthorhombic, Pbnm 4.56 10.70 2.85 

Monoclinic, B2,/d 8.88 5.25 5.71 



References 



Pyrolusite (p-MnOs) MnOa 

Ramsdellite Mn02 

Nsutite (r-MnOz) (Mn2*,Mn3*,Mn«*) (0,OH)2 

Hollandlte (a-MnOz) (Ba,K)i_2Mn80,6xH20 . . . . 



Cryptomelane Ki_2Mn80,6xH20 

Romanechite (psilomelane) (Ba,K,Mn^*,Co)2 Mn50,oxH20. . . 

Todorokite (Ca,Na,K,Ba,Ag,) (Mg,Mn='\Zn) 

Mn50,2xH20. 

Buserite NaMn oxide hydrate 

Chalcophanite Zn2Mn60i4-6H20 

Synthetic birnessite Na4Mn,4027-9H20 

Do Mn70,3-5H20 

Birnessite (Na,Ca,K) (Mg,Mn) Mn60,4-5H20. 

Vernadite' (&-Mn02) Mn02m(R20.RO,R203)nH20 . . 

Rancieite (Ca,Mn)Mn409-3H20 

Groutite a-MnOOH 

Manganite -y^MnOGH 



2 

4 

NA 
NA. 

na| 

NA-, 

na| 
na) 

NA 

NA 
NA 
NA 
NA 
NA 



NA 

NA 

NA 



70 

52, 56, 90, 1 1 1 

15 

52,56. 103 

4, 8, 70, 98 

3,66.70,72,90, 108, 

116, 119-120, 126 
7,21,53-58. 106 
34 

56, 129 
57 
7, 18,21,29-30, 37,40, 

58, 64, 70, 90, 108, 

116, 119-120 
7, 18, 22. 29-30, 106, 

108 
16, 116 
63, 103 
70 



NA Not available. NAp Not applicable 'R = Na, Ca, Co, Fe, Mn. 



12 




Figure 11. — Electron microscope observation of todorokite. Photograph courtesy of reference i7. 



specific positions in the chains of edge-shared [MnOe] 
octahedra. The larger Ca^*, Na , and related group I and II 
cations, together with water molecules, may occupy the large 
tunnel structure of todorokite. Some tunnel structures are 
disrupted by faults along the chain length with the faults 
going from triple to quadruple chains (126). Marine 
todorokites have been observed to contain quadruple, 
quintuple, and larger chains. Figure 12 shows the proposed 
atomic arrangement of one common structure for todorokite 
{126). 

Bimessite or 7-A Manganite 

Birnessite in manganese nodules is characterized by X-ray 
diffraction lines at 7.0 to 7.3 A and 3.5 to 3.6 A. Both sets of 
lines must be present to establish the presence of birnessite, 
because hollandite-cryptomelane, zeolites such as phillip- 
site, and clay-mica groups also have d-spacings around 7 A. 
The chemical formula for birnessite is Na4Mni4022-9H20 
(4 6); however. Burns and Burns (17) use 
(Na,Ca,K)(Mg,Mn)Mn60i4"5H20 as the marine form. The 
platy habit of birnessite observed by scanning electron 
microscopy is distinctive. 

The birnessite structure is postulated to contain layers of 
edge-shared [MnOe] octahedra separated by about 7.2 A 
along the c axis, which enclose sheets of H2O molecules. In 
synthetic sodium birnessite, one out of six octahedral sites in 
the layer of linked [MnOe] is unoccupied. The vacant Mn"* 



sites are distributed according to different patterns for 
adjacent [MnOe] octahedral layers, resulting in a two-layer 
orthorhombic cell with periodicity c = 14.26 A. The Mn^" and 
Mn^* ions are arranged above and below the vacancies, and 
are bonded with oxygens in both the [MnOe] layer and the 
sheet of H2O molecules. The structure of sodium-free 
birnessite has disordered vacancies in the [MnOe] layers, 
leading to a hexagonal cell with periodicity c = 7.27 A. 
Divalent cations of Cu, Ni, Co, Zn, etc. are located directly 
above and below vacancies in the edge-shared [MnOe] 
octahedral sheets, bound in the birnessite structure rather 
than randomly adsorbed on external surfaces of the 
microcrystallites. 

Vernadite or 6-Mn02 

The phase in manganese nodules giving only two diffuse 
X-ray diffraction lines at 2.40 to 2.45 A and 1 .40 to 1 .42 A is 
designated as vernadite, a poorly crystalline 8-Mn02 or 
supergene hydrated manganese (IV) oxide. The chemical 
composition of vernadite is variable, as reflected in its 
proposed formula: Mn02-m(R20, RO, R203)-nH20, where R 
= Na, Ca, Co, Fe, Mn (17). Fleischer (46) lists vernadite as 
(Mn*%Fe'*,Ca,Na)(0,OH)2-nH20. The iron observed to be 
present may be an intimately associated or epitaxial 
intergrowth of feroxyhyte, 6'-FeOOH, rather than a part of the 
vernadite structure. 

The vernadite is distinguished from a structurally dis- 



13 



TODOROKITE 




O • — Manganese 

O • — Oxygen 

(~^ ^^ — Tunnel cations or water molecules 

Figure 12 Proposed atomic arrangement for 

one common todorokite structure. 



ordered birnessite by its distinctive high specific surface area 
and its significant concentrations of Co, Ca, and Pb. The 
leaflets of vernadite are tens of angstroms smaller than 
flakes of birnessite, and are often curved and folded to 
resemble fibers. 

The vernadite structure is represented as a two-layer 
hexagonal packing of oxygen atoms and water molecules in 
which the octahedra are completely filled, but less than half 
with the tetravalent manganese. The extent of filling by Mn"* 
is apparently determined by the contents of water and 
cations other than Mn' * . By inclining leaflets of vernadite with 
respect to the electron beam, reflections with d spacing equal 
to 2. 18 to 2.20 A, corresponding to the (101) plane, lead to an 
approximate c parameter of 4.7 A. This is the approximate 
width of two layers of close-packed oxygens. 

The poor crystallinity and high specific surface areas of 
vernadite result in this phase having high cation adsorption 
properties, particularly tor cobalt. The substitution of low-spin 



Co'* (ionic radius 0.53 A) for Mn"* (0.54 A) in the [MnOe] 
octahedra of vernadite has been confirmed by photoelectron 
spectroscopy (100). 

Other Manganese Minerals 

Other manganese minerals that have been reported in 
manganese nodules are listed in table 2. These include 
pyrolusite or p-Mn02, ramsdellite, nsutite or 7-Mn02, 
hollandite or a-MnOg, cryptomelane, romanechite or psi- 
lomelane, chalcophanite, rancieite, groutite, and manganite. 
However, they do not appear to be common, and some 
identifications are not fully accepted. A good discussion of 
these minerals and others is found in the review by Burns 
and Burns {15, 17). 

Manganese Mineral-Element Association 

Several elements are associated solely with the man- 
ganese mineral phase of the nodule. Other elements have 
been shown to exist with the manganese mineral phase and 
with the iron or accessory mineral phases. Those elements 
associated almost entirely with the manganese mineral 
phase are Cu, Mo, Ni, and Zn. Other elements associated 
with the manganese phase, but which may be found in other 
phases also, are Ba, Cd, Ca, Mg, Sb, Sr, and V. 



IRON OXIDE MINERALS 

The oxide, oxide hydroxide (or oxyhydroxide), and 
hydrated oxide phases of iron relevant to manganese nodule 
mineralogy are listed in table 3. Included in table 3 are the 
crystallographic data and some of the literature references to 
the occurrence of each iron oxide mineral in manganese 
nodules. As stated earlier, the information to date is based on 
limited studies, and identification of these iron minerals is 
difficult because they are extremely fine grained. By analogy 
with the manganese oxides, the structures of many of the 
iron oxides consist of close-packed oxygens containing Fe^' 
and/or Fe^* ions in various octahedral interstices forming 
different assemblages of edge-shared [FeOe] octahedra. 
Certain iron (III) oxide hydroxides are isostructural with 
manganese (IV) oxides, with [FeOe] and [MnOe] octahedra 
edge-shared in different arrangements. The larger ionic 
radius of Fe^_compared with Mn' results in larger spacings 
for the (1010) and (1120) planes of the hexagonal 
close-packed systems (approximately 2.50 to 2.56 A and 
1.48 to 1.54 A, respectively), and Fe-Fe interatomic 
distances across edge-shared [Fe(0,0H)6] octahedra range 
from 2.95 to 3.05 A. The most commonly observed 
iron-bearing minerals in manganese nodules, to be discus- 
sed in more detail, are goethite, lepidocrocite, and feroxy- 
hyte. Other iron minerals observed include akaganeite, 
ferrihydrite, hematite, magnetite, and maghemite. 



Table 3. — Iron oxide minerals in Pacific manganese nodules 



Mineral 

Goethite (a-FeOOH 

Akaganeite (p-FeOOH) 

Lepidocrocite (7-FeOOH) 

Hydrated oxyhydroxide 
polymer (synthetic). 

Ferrihydrite 

Feroxyhyte (fi'-FeOOH) 

Hematite (u-FesOs) 

Maghemite (^'-FejOs) 

Magnetite (spinel) 

NA Not available. NAp Not applicable 



Approximate formula 



Crystal system and 
space group 



Cell parameters, A 



References 



FeOOH Orthorhombic, Pbnm 4.65 

(OH,CI,H20),^2 Fe8(0,OH),6 . . Tetragonal, 14/m 10.48 

FeOOH Orthorhombic, Amam 3.88 

rFeO,3_,| 2(0H), Hexagonal. NA 5.88 

lFe5H08-4H20 Hexagonal, NA 5.08 

SFesOa-SHaO Hexagonal, NA 5,08 

FeOOH Hexagonal. NA 2 93 

Fe203 Hexagonal, R3c 5,04 

FesOs /Cubic, P2,3 8,32 

iTetragonal, P4,2,2 8.338 

Fe304 Cubic, Fd3m 8.39 



10,02 
10.48 
12.54 
NAp 
NAp 
NAp 
NAp 
NAp 
8.32 



3.04 
3,028 
3.07 
9.4 
9,4 
9,4 
4,60 
13,77 
8,32 



8 338 25,014 
839 8,39 



4 

1 

4 

NA 
NA 
NA 

1 

6 

S) 
NAJ 

8 27 



22, 27, 51. 62, 78 
61 

27, 35, 51, 62, 78 
71, 75-77 

28, 129 
23 
36 
69 
27, 62, 



129 



14 



Feroxyhyte 

Feroxyhyte is considered to be a polymorph with 
akaganeite, goethite, and lepidocrocite and has a formula of 
8'-FeOOH (36). The structure is thought to be a hexagonal 
close packing of oxygen and differs only from 8-FeOOH by 
the arrangement of the iron atoms. Feroxyhyte is found as 
yellow-brown plates in admixtures of clay minerals and 
goethite. Its strongest diffraction lines are 2.54 and 2.23 A, 
with other lines at 1 .69 and 1 .47 A {36). 

As a magnetically disordered form of 8-FeOOH, no 
reflection characterizing an ordered distribution of Fe^* in the 
octahedral sites is observed in electron diffraction patterns 
from feroxyhyte. Feroxyhyte is unstable in air and transforms 
to goethite {99). 

Goethite 

Goethite (a-FeOOH) is the polymorph to which most other 
FeOOH phases revert upon aging. It is isostructural with the 
manganese minerals ramsdellite and groutite, consisting of 
double chains of [Fe(0,0H)6] octahedra linked together by 
sharing opposite edges. An octahedron from one chain 
shares an edge with two octahedra from another chain, and 
the double chains are further crosslinked to adjacent double 
chains through double sharing of oxygen, producing an 
orthorhombic symmetry. The goethite in this structure occurs 
in a habit of acicular needles, 0.1 to 1.0 (xm in length. The 
iron atoms occupy only octahedral positions in this yellow- 
brown colored mineral {99). 

Goethite is an antiferromagnetic mineral, that is, goethite 
remains magnetized even when a magnetic field is removed. 
The magnetization is not reversible. High CI concentrations 
in seawater should inhibit the formation of goethite. Thus, the 
widely reported occurrence of goethite in nodules may result 
from the fact that it is the end product of both hydrolysis and 
oxidation action in the other FeOOH phases {99). 

Lepidocrocite 

The abundance of reported lepidocrocite (7-FeOOH) 
appears to indicate a relatively rapid oxidation of Fe(ll) 
solutions, though it may occasionally form from Fe(lll). 
Lepidocrocite has a cubic close-packed oxygen lattice 
structurq with no structural analogs among the manganese 
oxides or hydroxide phases. The iron atoms occupy only 
octahedral positions in the stacking of oxygen-hydroxyl 
planes along the [051] direction. This orange-colored mineral 
forms lath-shaped crystals ranging from 0.5 to 1 .0 ixm long 
199). 

Lepidocrocite is neither ferrimagnetic nor antiferromagne- 
tic (see appendix) at ordinary temperatures, and so it carries 
no magnetic remnants. It is transformed to maghemite at 
250° to 300° C. 

Other Iron Oxide Minerals 

Akaganeite (p-FeOOH) is the form of iron that precipitates 
from Cl-rich solutions such as seawater. The failure to 
identify akaganeite more frequently in nodules may be the 
result of rapid conversion to the more stable goethite under 
seawater conditions, though akaganeite has been shown to 
be stable for up to 2 yr at pressures up to 1,000 atm {99). 
Also, the cryptocrystallinity of akaganeite may have resulted 
in the mineral being amorphous to X-ray diffraction, or 
phases identified as phillipsite may have actually been 
mixtures of goethite and akaganeite (99). 

Magnetite (Fe304) and maghemite (7-Fe203) result from 
relatively slow oxidation of Fe(ll) solutions, and can form 
authigenically in the ferromanganese nodules. Hematite can 
crystallize from the seawater dissolution of fine-grained 
goethite or by dehydration of the goethite, but environmental 
conditions may result in the formation of both minerals by 



separate pathways. Hematite, once formed, does not appear 
to rehydrate to form goethite. Hematite is also formed by the 
aggregation of small ferrihydrite particles followed by 
nucleation and crystallization of hematite. Ferrihydrite also 
serves as a source of dissolved iron for the crystallization of 
goethite. 

Iron Oxide Mineral-Element Association 

Several elements are associated solely with the iron oxide 
phase of the nodule. Other elements have been shown to 
exist in iron oxide mineral phases and with manganese or 
accessory mineral phases. Those elements associated 
almost entirely with the iron oxide phase are Pb and Ti with 
Co occurring in both the iron and manganese phase 
depending on the oxidation-reduction potential of the 
seafloor (generally related to depth). Other elements 
associated with the iron phase, but which may also be found 
in other phases, are Ce, Co, Sr, V, and Zr. 



ACCESSORY MINERALS 

The accessory minerals found in Pacific manganese 
nodules can be divided into the following three general 
categories: 

1 . Sheet silicates and zeolite minerals. 

2. Clastic silicate and volcanic minerals. 

3. Biogenic minerals. 

These minerals are poorly defined in manganese nodules 
because most exist as fine-grained crystallites similar to the 
manganese- and iron-phase minerals. Some of these 
accessory minerals were identified in the residues of acid 
leached nodules. This acid leaching tends to concentrate, 
and potentially recrystallize and/or flocculate these minerals 
together with the iron-phase minerals while dissolving the 
manganese-phase minerals. Because of their low concen- 
trations in nodules, the accessory minerals are often not 
detected by X-ray diffraction methods on bulk samples. 
Some minerals have been identified by selective area 
electron diffraction. 

Although most published studies on manganese nodules 
do not address the accessory minerals, some of these 
minerals may be necessary for the nucleation and growth of 
the iron and manganese oxides. Quite often, the core or 
nucleus of nodules consists of volcanic rock fragments, 
glass, shark teeth, fish bones, or siliceous and calcareous 
remains of marine organisms. Table 4 lists the various 
accessory minerals, their formulas, cell parameters, crystal 
system, and references where they were reported. 

Sheet Silicates and Zeolites 

Several sheet silicates and zeolites have been reported in 
manganese nodules. The clay found in nodules are those 
associated with the sediments where the nodules were 
formed {19-20), and are fine-grained hydrous aluminum 
silicates probably formed by submarine alteration of the 
primary minerals in basalts. The sheet silicates reported in 
nodules are chlorite, illite, kaolinite, montmorillonite, nontro- 
nite, pyrophyllite, and talc. The common clay present is 
generally montmorillonite. These minerals in nodules occur 
probably from inclusion of the sediments during nodule 
growth. 

The zeolites found in nodules are authigenic and are found 
in cracks and cavities in the interior of nodules. The zeolites 
are hydrous silicates with a very open framework and large 
interconnecting spaces or channels that are filled with 
sodium, calcium, and variable amounts of water. The zeolites 
reported in nodules are analcite, clinoptilolite, epistilbite, 
erionite, mordenite, and phillipsite. The most commonly 
reported zeolite is phillipsite whereas the remaining zeolites 



15 



Table 4. — Accessory minerals in Pacific manganese nodules 



Mineral group and mineral 



Formula 



Crystal system and 
space group 



Cell parameters, A 



References 



SILICATES 



Tectosilicates: 
Zeolites: 

Analcite NaAISi206H20 Isometric, Ia3d 13.72 

Clinoptilolite (Na,K,Ca)2-3Al3(AI,Si)2Si,3036-12H20 Monoclinic, 12/m 15.85 

Epistilbite CaAlsSigOis-SHsO Monoclinic. NA 8.92 

Erionite (Ca,Na,K,Mg)5Al9Si27072-27H20 Hexagonal, PSa/mmc 13.26 

Mordenite (Ca,N'a2,K2)4AleSi4o096-28H20 Orthorhombic, Cmcm 18.13 



Phillipsite KCa(Al3Si50,6)-6H20 Orthorhombic, B2mb 

Do Kj aNa, eAU 4S1, , 6032-1 OH2O Monoclinic, P2, or P2i/m . 

K-feldspar (orthoclase) KAISijOg Monoclinic, C2/m 

Labradorite (feldspar) Ab^oAnso^^^-AbsoAnyo Triclinic, NA 

Plagioclase (feldspar) (Na,Ca)AI(Si,AI)Si208 Triclinic, NA 

Sanidine (feldspar) KAISi308 Monoclinic, C2/m 

Quartz 8102 Hexagonal, P3221-P3,21 



9.96 
10.02 
8.56 
8.17 
8.14 
8.56 
4.91 



Phyllosilicates: 

Chlorite (Mg,Fe)3(Si,AI)40,o(OH)2(Mg,Fe)3(OH)6 Monoclinic, C2/m 5.2 

lllite General term for mica-like clays NAp NAp 

Kaolinite Al2Si205(OH)4 Triclinic, PI 5.14 

Montmorillonite (AI,Mg)8(Si40,o)3(OH)io-12H20 Monoclinic, C2/m 5.23 



Nontronite Fe2(AI,Si)40io(OH)2Nao 3(H20)4 M loclinic, NA . 



5.23 



Pyrophyllite Al2Si40,o(OH)2 Monoclinic, C2/c 5.16 

Talc Mg3Si40io(OH)2 Monoclinic, C2/c 5.27 

Biotite (mica) K(Mg,Fe)3(AISi30,o)(OH)2 Monoclinic, C2/m 5.31 

Prehnite Ca2AI(AISi30,o)(OH)2 Orthorhombic, P2c/m 4.65 

Stilpnomelane K(Fe,Mg,AI)3Si40,o(OH)2xH20 Monoclinic, NA 5.40 

Inosilicates (double chain): 

Hornblende (amphibole) . . . (Ca,Na)2-3(Mg,Fe,AI)5Si6(SiAI)2022(OH)2 Monoclinic, C2/m 9.87 

Inosilicates (single chain): 

Augite (pyroxene) (Ca,Na)(Mg,Fe,AI)(Si,AI)206 Monoclinic, C2/c 9.73 

Nesosilicates: Olivine (Mg,Fe)2Si04 Orthorhombic, Pmcn 4.76- 

4.82 

Other silicates: 

Opal (amorphous) Si02-nH20 NAp NAp 

Titanite (sphene) CaTiOOiOs) Monoclinic, C2/c 6.56 



13.72 
17.89 
17.73 
NAp 
20.49 
14.25 
14.28 
12.96 
12.85 
12.84 
13.03 
NAp 



9.2 

NAp 

8.93 

8.93- 

9.00 

9.10- 

9.12 

8.88 

9.12 

9.23 

5.48 

9.42 

18.01 



13.72 
7.41 

10.21 

15.12 
7.52 

14.25 
8.64 
7.21 
7.13 
7 16 
7.17 
5.41 



28.6 
NAp 
7.37 

29.8 

NA 

18.64 
18.85 
10.18 
18.49 
12,14 

5.33 



16 
4 
3 

NA 

4 

4 

NA 
8 
4 
3 



4 
NAp 

2 
NA 

NA 

2 

4 
2 
2 
1 



8.91 5.25 



10.20- 
10.48 

NAp 
8.72 



5.98- 
6.11 

NAp 
7.44 



NAp 
4 



70 
94 
94 
94 

3, 94 

3-4, 11, 65, 
104-106, 115 

11, 22, 115 

11 

94, 115 

94 

5, 11, 22, 24, 62, 
70, 104-106, 
115, 121 

4, 1 1 , 24 
94, 115, 121 
106, 115 

3-4, 6, 11, 58, 65, 
94, 105, 129 

5, 11, 93, 106 

94 
94 
93 
94 
106 

5,93 

5,11, 70, 93-94, 

106 
11, 94 



5, 93 
14 



NONSILICATES 



Volcanics: 

Anatase Ti02 

Barite BaS04 

Ilmenite FeTiOs 

Magnetite (spinel) (Fe,Mg)Fe204 

Rutile Ti02 

Biogenics: 

Apatite Ca5(P04)3(F,CI,0H). 

Aragonite CaCOs 

Calcite CaCO, 



. Tetragonal, 14,/amd 3.78 3.78 9.51 4 5, 70, 93 

. Orthorhombic, Pnma 8.87 5.45 7.14 4 5, 70, 93 

. Hexagonal, R3 5.09 NAp 14.06 6 94 

. Isometric, Fd3m 8.40 8.40 8.40 8 94 

. Tetragonal, P42/mnm 4.59 4.59 2.96 2 5, 70, 93 

. Hexagonal, P63/m 9.39 NAp 6.89 2 4-5, 9, 90 

. Onhorhombic, Pmcn 4.95 7.96 5.73 4 92 

. Hexagonal, R3c 4.99 NAp 1 7.06 6 72, 90 



NA Not available. NAp Not applicable. 



are rare with some question of their proper identification. 
Phillipsite, because of its delicate euhedral crystal habit and 
its occurrence in the leached interior cavities of nodules 
appears to have formed authigenically (fig. 13). Phillipsite 
crystals in some nodules appear to have grown together with 
some of the manganese oxide phase minerals, particularly 
todorokite (19-20). 

Clastic Silicates and Volcanics 

Many silicate minerals and some volcanic minerals have 
been observed in manganese nodules. They consist of 
individual grains of clastic sediments of various minerals that 
may form the core or become incorporated into the nodule 
during nodule growth. The clastic silicate (detrital) minerals 
observed in nodules are given in table 4. The more common 
minerals present are quartz and various feldspars. One 
mineral, opal, is believed to have formed authigenically. The 
volcanic minerals reportedly observed in manganese 
nodules are barite, magnetite (spinel), and the titanium- 
containing minerals, anatase, ilmenite, rutile, and sphene. 



Biogenics 

The biogenic minerals found in manganese nodules come 
from the debris of dead organisms, such as bones and teeth 
of fish, sharks, and whales, and the siliceous remains of the 
zooplankton radiolaria. The larger debris such as bones and 
teeth are generally associated with the cores of nodules 
whereas the radiolaria remains are observed throughout the 
nodules. These radiolaria remains are probably incorporated • 
from the sediment as the nodule grows. The debris in the 
interior of the nodule may undergo dissolution and may be 
associated with the formation of phillipsite and todorokite. 
The minerals of biogenic origin are apatites, primarily from 
bones and teeth; aragonite and calcite, from the shells of 
various animals; and opal, which may also be derived from 
radiolaria. 

Sea Salt Residue 

f^inerals in dried nodules that are the result of seawater 
evaporation are sylvite, halite, and other common evaporites 



16 




Figure 1 3. — Scanning electron photomicrograph showing crystals of the zeolite phillipsite in an oxide 

cavity off a manganese nodule. Photograph courtesy of reference 117, p. 60. 



17 



present in dissolved form in seawater. These residues are 
also the primary source of the anions — borate, bromide, 
chloride, fluoride, and iodide — in manganese nodules. 

Accessory Mineral- 
Element Association 

Several elements are associated solely with the accessory 
minerals of the nodule. Other elements have been shown to 
exist in accessory minerals and with the iron oxide or 
manganese phases. Those elements associated almost 
entirely with the accessory minerals are Al, Cr, K, P, and Si. 



Other elements associated with the accessory minerals and 
possibly other phases are Ba, Mg, Na, and Zr. 



MOISTURE CONTENT 

Water in manganese nodules comprises about 45 to 50 
wt-pct of the nodule when removed from the sea. Drying in air 
removes approximately half of the water. Drying at 110° C 
reduces the moisture content of nodules to approximately 5 
to 10 wt-pct. Thermal gravimetric analysis in the temperature 
range of 110° to 1,200° C indicates that the 5 to 10 wt-pct 
water is bound in the crystal structure. 



ELEMENTAL COMPOSITION 



The elemental characterization of Pacific manganese 
nodules is a topic addressed by many authors. Major 
element composition of these nodules is well established, 
whereas data on many minor and most trace elements are 
limited. This section summarizes available data on most of 
the naturally occurring elements, and where data are 
sufficient, gives ranges, means, medians, and number of 
samples. In the case of the major, most minor, and some 
trace elements, the data are divided into four distinct areas of 
the Pacific Ocean floor. 

1. The Clarion-Clipperton Fracture Zone area (CC-Zone 
area). 

2. The mid-Pacific seamounts area (MPS area), <3,000- 
m depth. 

3. Other abyssal plains area >3,000-m depth, and 
exclusive of CC-Zone area. 

4. Other seamounts, ridges, and continental margins area 
(<3,000-m depth). 

For these elements, histograms and comparison tables are 
presented for the different areas to show variations of these 
elements by area. Where a paucity of data exists for the 
remaining elements, histograms, and tables are presented 
for the composition based on the total Pacific Ocean, In some 
cases, data are so limited (<40 sample analyses) that no 
histogram is presented. Nodules from the Drake Passage 
area of the Pacific and most of the ocean area directly south 
of Australia have also been omitted. The Drake Passage 
nodules are omitted because of their tendency to contain 
large rock fragments as nuclei, thereby making their bulk 
chemical analysis atypical of the other Pacific nodules. The 
area south of Australia is the southeast portion of the Indian 
Ocean and therefore is not considered part of the Pacific 
Ocean. 

The data for the elements are broken down into eight 
groups based on either their chemistry or special interest. 
The groups of elements are presented in the following order: 

1. Major and minor elements of potential economic 
interest (Mn, Fe, Ni, Cu, Co, Zn, V, Mo). 

2. Other major and minor elements (Al, Ca, Mg, K, Si, Na, 
Sr, Ti, Zr). 

3. Elements of environmental interest (As, Ba, Cd, Cr, Pb, 
Hg, Se, Ag). 

4. Rare-earth elements (lanthanides) (La, Ce, Pr, Nd, Sm, 
Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf). 

5. Precious-metal-group elements (Au, Ir, Pd, Pt, Re, Ru). 

6. Radioactive elements (Ra, Th, U). 

7. Other trace elements (Sb, Be, Bi, B, Cs, Ga, Ge, Li, 
Nb(Cb), Rb, Sc, Ta, Te, TI, Sn, W, Y). 

8. Anion-forming elements (Br, C, CI, F, I, N, P, S). 

Within the first three groups, each element is discussed 
briefly; the chemical form of occurrence in nodules is given if 



known, and for 21 elements listed within the first three 
groupings (exclusive of Ag, As, Hg, and Se), interelement 
correlations are presented by area where data are sufficient. 
The interelement correlation coefficients (presented in table 
19) are results of linear regression analysis with the 
correlation coefficients varying from - 1 to + 1 . Correlations 
with values >0.3 and <-0.3 were considered significant 
positive or negative correlations. Of the naturally occurring 
elements (exclusive of inert gases and hydrogen), no data 
were obtained for the following elements: Rh, In, Pm, Os, Po, 
At, Fr, Ac, and Pa. Oxygen is not discussed specifically but is 
the major combining form for most elements. All concentra- 
tions are reported on a dry-weight basis. The majority of the 
information contained in these sections was obtained from 
the Sediment Data Bank (48), as compiled by Frazer with 
information from Frazer (44, 48-50), Sorem (118), Fewkes 
(42-43), and Monget (97). 



MAJOR AND MINOR ELEMENTS OF 
POTENTIAL ECONOMIC INTEREST 

The elements in this section are those major and minor 
elements that are of potential economic interest. The eight 
elements are Mn, Fe, Ni, Cu, Co, Zn, V, and Mo. Because of 
the amount of data available, the concentrations of these 
elements are divided into the four areas of the Pacific 
previously mentioned. Table 5 is a breakdown, by element, 
for the four areas, and gives range, median range, arithmetic 
mean, standard deviation of the mean, and the number of 
samples used for the statistical base. Table 6 gives 
composite data for those elements from Pacific nodules. The 
overall mean in table 6 is calculated based on the number of 
data points for each element in each area and the respective 
concentrations. 

Manganese 

Manganese concentrations in Pacific nodules vary from 1 
to 40 wt-pct, with a median range of 16 to 27 wt-pct, and 
weighted mean of 21.6 wt-pct based on 5,079 sample 
analyses. The median value for CC-Zone area nodules is the 
highest of all other areas at 26 to 27 wt-pct with a mean of 
25.4 wt-pct. Nodules from the other three areas are much 
lower with a median range of 1 6 to 21 wt-pct and much higher 
iron values. Figure 14 provides histograms that show 
manganese distribution in each of the four areas. 

Manganese occurs in Pacific nodules as several minerals, 
all oxides and hydrated oxides. These minerals are 
todorokite, birnessite, and vernadite (S-MnOg). A discussion 
of these and other forms of manganese is given in detail in 
the "Mineralogy" section. 

Manganese in the CC-Zone area is positively correlated 



Table 5 Distribution off elements off potential economic interest in Paciffic manganese nodules, by 

area, weight-percent 



Area 



Range 



Median 



Mean, 



Standard 

deviation of 

mean, ctx 



Number of 
samples 



Range 



Median 



Mean, 

X 



Standard 

deviation of 

mean, o-x 



Number of 
samples 



Clarlon-Cllpperton zone 

MId-PaclfIc seamounts 

Other abyssal plains, >3,000 m. 
Other seamounts, ■<3, 000 m . . . 

Clarlon-Clipperton zone 

MId-PaclfIc seamounts 

Other abyssal plains, >3,000 m. 
Other seamounts, < 3,000 m . . . 

Clarlon-Cllpperton zone 

Mid-Pacific seamounts 

Other abyssal plains, >3,000 m. 
Other seamounts, <3,000 m . . . 

Clarlon-Cllpperton zone 0.10- 2.00 

MId-PaclfIc seamounts <.01- 1 .00 

Other abyssal plains, >3,000 m. . . . <.05- 2.00 

Other seamounts, <3,000 m <.05- 1.20 











Manganese 














Cobalt 






1 


-39 


26 


-27 




25.4 


4.9 


2,227 


<0.10-0.90 


0.20-0.30 


0.24 


0.08 


1,925 


1 


-40 


20 


-21 




20.8 


8.1 


183 


<. 10-2.50 


.70- 


.80 


.76 


.45 


182 


1 


-40 


18 


-19 




18.5 


7,2 


2,354 


<. 10-1 .40 


.20- 


.30 


.24 


.17 


2,219 


1 


-40 


16 


-17 




17.8 


8.6 


315 


<. 05-1 .40 


.20- 


.30 


.31 


.27 


293 


Iron 


Zinc 


1 


-25 


6 


- 7 




6.9 


2.6 


2,215 


<0.05 -0.95 


0.10-0.15 


0.14 


0.05 


1,539 


2 


-25 


14.5 -15.5 


14.7 


4.1 


185 


<.05 - 


.25 


.05- 


.10 


.07 


.03 


82 


1 


-25 


12 


-13 




12.7 


5.1 


2,325 


<.05 - 


.95 


.05- 


.10 


.09 


.1 


1,285 


1 


-25 


16 


-17 




15.6 


6.4 


312 


<.05 - 


.55 


.05- 


.10 


.07 


.05 


191 


Nickel 


Vanadium 


0.10- 2.00 


1.30- 1.40 


1.28 


0.30 


2,237 


<0.005-0.08 


0.04-0.05 


0.047 


0.048 


70 




10- 1.50 




40- 


50 


.49 


.24 


188 


<.005- 


.30 


.07- 


.08 


.086 


.087 


29 




10- 2.00 




50- 


60 


.63 


.40 


2,334 


<.010- 


.30 


.04- 


.05 


.048 


.025 


370 




10- 1.30 




30- 


40 


.35 


.24 


315 


<.005- 


.14 


.06- 


.07 


.067 


.028 


38 


Copper 


Molybdenum 



1.00-1.10 1.02 

<.05 .10 

.30- .40 .42 

<.05 .11 



0.33 
.10 
.32 
.14 



2,236 
176 

2,282 
304 



<0.005-0.12 0.05-0.06 0.052 0.018 265 

<.005- .11 .05- .06 .052 .022 56 

<.005- .13 .03- .04 .036 .021 746 

<.005- .15 .03- .04 .050 .067 88 



Table 6. — Distribution off elements of potential 

economic interest in Paciffic manganese 

nodules, composite, weight-percent 



Element 



Range 



Range of 
medians 



Weighted 
mean 



Number of 
samples 



Manganese 1 -40 

Iron 1 -25 

Nickel 1 - 2.0 

Copper < .01 - 2.0 

Cobalt < .05 - 2.5 

Zinc < .05 - .95 

Vanadium < .005- .30 

Molybdenum < .005- .15 



16 -27 


21.6 


5,079 


6 -17 


10.4 


5,037 


.3 - 1.4 


.9 


5,074 


.05- 1.10 


.66 


4,998 


.2 - .8 


.26 


4,619 


.05- .15 


.11 


3,097 


.04- .08 


.05 


507 


.03- .06 


.04 


1,157 



(table 19) with Cd, Cu, Mg, Mo, Ni, Sr, V, and Zn, and is 
negatively correlated with Al, Fe, K, Na, Si, and Ti. In the 
MPS area, manganese shows a positive correlation with Co, 
Mo, Ni, Pb, Sr, Zn, and Zr, and a negative correlation with Al 
and Ca. In the other abyssal plains area, manganese is 
positively correlated with Cd, Cu, Mo, Ni, and Zn, and 
negatively correlated with Al, Fe, K, and Si. In the other 
seamounts area, manganese is positively correlated with Ba, 
Na, and Ni, and negatively correlated with Al, Cd, and Fe. 
Where elements are not mentioned, no correlation (<0.3 to 
>-0.3) was obtained. A positive correlation of manganese 
with Cu, Ni, Mo, and Zn and a negative correlation of 
manganese with Al and Fe are observed in all areas. The 
difference in elemental composition between the lesser 
depths (MPS and other seamounts) and greater depths (CC 
Zone and other abyssal plains) may reflect differences in 
oxidation potential as well as sediment type. 

Iron 

Iron concentrations in Pacific nodules vary from 1 to 25 
wt-pct, with a median range of 6 to 1 7 wt-pct and a weighted 
mean of 10.4 wt-pct based on 5,037 sample analyses. The 
median value for CC-Zone area nodules is lowest of all areas 
at 6 to 7 wt-pct with a mean of 6.9 wt-pct. The other three 
areas are much higher in iron with a median range for these 
areas of 12 to 17 wt-pct. Figure 15 provides histograms that 
show iron distribution in each of the four areas. Iron occurs in 
Pacific nodules as goethite and other iron oxides and 
hydrated oxides as discussed in the "Mineralogy" section. 



Iron in CC-Zone nodules is positively correlated (table 19) 
with Co, Pb, Ti, and Zr, and negatively correlated with Cd, 
Cu, Mg, Mn, Mo, Ni, and Zn. In the MPS area, iron is 
positively correlated with Ti and Zr, and negatively correlated 
with Ba and Ca. In the other abyssal plains area, iron is 
positively correlated with Co, Pb, Sr, Ti, V, and Zr, and 
negatively correlated with Cd, Cu, K, Mn, and Ni. In the other 
seamounts area, iron is positively correlated with Cr, Ti, V, 
and Zr, and negatively correlated with Ba, Ca, and Mn. 

Nickel 

Nickel concentrations in Pacific nodules vary from 0.1 to 
2.0 wt-pct, with a median range of 0.3 to 1 .4 wt-pct and a 
weighted mean of 0.9 wt-pct based on 5,074 sample 
analyses. The median value for CC-Zone area nodules is 1 .3 
to 1 .4 wt-pct with a mean of 1 .3 wt-pct. The other three areas 
are much lower in nickel content with a median range of 0.3 
to 0.6 wt-pct. Figure 16 provides histograms that show nickel 
distributions for each of the four areas. 

Nickel occurs in Pacific nodules as part of the manganese 
mineral structure probably adding stability to the minerals. 
The nickel is strongly correlated with manganese in all areas 
of the Pacific. The ionic radius of Ni^* allows for direct 
substitution of Ni^* for Mn^* in the crystal structures. 

Nickel in CC-Zone area nodules is positively correlated 
(table 19) with Cd, Cu, Mg, Mn, Mo, Sr, V, and Zn, and 
negatively correlated with Fe, Si, and Ti. In the MPS area, 
nickel is positively correlated with Co, Cr, Mg, Mn, Mo, Na, 
and Zn, and negatively correlated with Al only. In the other 
abyssal plains area, nickel is positively correlated with Cd, 
Cu, Mn, Mo, and Zn, and negatively correlated with Fe and 
Si. In the other seamounts area, nickel is positively correlated 
with Cd, Co, Cu, Mg, Mn, and Zn, and no negative 
correlations are found. 

Copper 

Copper concentrations in Pacific nodules vary from <0.01 
to 2.0 wt-pct with a median range of <0.05 to 1 .1 wt-pct and a 
weighted mean of 0.66 wt-pct based on 4,998 sample 
analyses. The median value for CC-Zone area nodules is 1 .0 
to 1 .1 wt-pct with a mean of 1 .0 wt-pct. The other three areas 
are much lower in copper with a median range of <0.05 to 
0.4 wt-pct. Figure 17 provides histograms that show copper 
distribution in each of the four areas. 



19 



270 



243 



216 



189 



162 



135 



108 



27 



Tf K^ 



12 



18 24 30 

Mn-CC ZONE, pet 



42 



ID - 


I 1 I- 


1 1 1 ■ 


14 - 




r 


12 ' 




-| 


10 - 




-1 


8 - 
6 - 


r 


r-i 


4 - 
2 - 


rn n r ttt 


- -| p 


PI 



6 12 18 24 30 36 42 

Mn-MID-PACIFIC SEAMOUNTS, pel 



210 



189 



168 



147 



£ 126 - 



105 



= 84 
O 



63 



42 



24 



^rm r^ 



o 

!?i 15 



O 

o 
o 

LL 12 



3 - 



36 42 



6 12 18 24 30 36 42 6 12 18 24 30 

Mn-OTHER ABYSSAL, pel Mn-OTHER SEAMOUNTS, pel 

Figure 14. — Manganese frequency distribution by environment for Pacific manganese nodules. 



20 



520 



468 



416 



364 



260 



208 



156 



104 



52 



-I 1 1 r 



ttu 



8 12 16 20 24 

Fe-CC ZONE, pet 



28 



27 



24 



18 



7? 15 



12 



u. 9 



1 1 1 1 1 1 1 1 


III' 



8 12 18 20 

Fe-MID-PACIFIC SEAMOUNTS, pet 



24 28 



230 



27 



24 - 



21 - 



8 '' 



12 - 



a 

I 9 






6 - 



3 - —I - 



207 



184 



161 



U 

ui 138 



115 



uj 92 



46 - ^ 



23 



4 8 12 16 20 24 28 4 8 12 16 20 24 28 

Fe-OTHER SEAMOUNTS, pet Fe-OTHER ABYSSAL, pet 

Figure 1 5. — Iron frequency distribution by environment for Pacific manganese nodules. 



21 



32S 



246 



123 




0.6 0.9 1.2 1.5 

Ni-CC ZONE, pel 



15 ^ 



n n 

0.6 0.9 1.2 1.5 

Ni-MID-PACIFIC SEAMOUNTS. pel 



310 



248 



217 



62 























1 1 1 1 


56 










- 


49 


- 








- 


42 


- 








- 


35 


- 








- 


28 


- 












- 


21 


- 












- 




















14 


- 














- 


7 










_ 






- 




-n 


1 — 1 



0.3 



1.8 



0.6 0.9 1.2 1.5 1.8 2.1 0.3 0.6 0.9 1.2 1.5 

Ni-OTHER ABYSSAL, pet Ni-OTHER SEAMOUNTS, pel 

Figure 16. — Nickel frequency distribution by environment for Pacific manganese nodules. 



2.1 



22 



350 



315 



280 



245 



= 210 
O 

o 
o 



140 



105 



70 



35 - 



-) 1 1 r r- 



0.3 0.6 0.9 1.2 1.5 

Cu-CC ZONE, pel 



1.8 2.1 



480 



432 



384 



336 



288 



240 



^ 192 
O 



144 



96 



48 



J 



108 



n 



96 



4 



60 I 



y 48^ 



24 



12 



190 



171 



152 



133 



S 114 



o 
o 
o 

u. 95 
O 



U 



76 ^ 



57 



38 



19 



0.3 0.6 0.9 1.2 1.5 1.8 

Cu-MID-PACIFIC SEAMOUNTS, pet 



0.3 0.6 0.9 1.2 1.5 1.8 2.1 

Cu-OTHER ABYSSAL, pel 



2.1 



0.3 0.6 0.9 1.2 1.5 1.8 2.1 

Cu-OTHER SEAMOUNTS, pet 

Figure 1 7. — Copper frequency distribution by environment for Pacific manganese nodules. 



23 



Copper occurs in Pacific nodules in a manner similar to 
that of nickel, which is part of the manganese mineral 
structure with no copper minerals present. The ionic radius of 
Cu^' allows direct substitution for Mn^- in the manganese 
minerals crystal structures. 

Copper in CC-Zone area nodules is positively correlated 
(table 19) with Al, Cd, Mg, Mn, Mo, Ni, Sr, V, and Zn, and 
negatively correlated with Fe, K, Na, Pb, Si, Ti, and Zr. In the 
MPS area, copper is positively correlated with Cr only and 
negatively correlated with Al and Zr. In the other abyssal 
plains area, copper is positively correlated with Cd, Mn, Ni, 
and Zn, and negatively correlated with Fe and Pb. In the 
other seamounts area, copper is positively correlated with 
Cd, Mg, Ni, V, and Zn, and shows no negative correlation 
with the other elements. 

Cobalt 

Cobalt concentrations in Pacific nodules vary from <0.05 
to 2.5 wt-pct, with a median range of 0.2 to 0.8 wt-pct and a 
weighted mean of 0.26 wt-pct based on 4,619 sample 
analyses. The median value for CC-Zone area nodules is 0.2 
to 0.3 wt-pct with a mean of 0.24 wt-pct. Cobalt values are 
lowest in the two deep-ocean areas (CC Zone and other 
abyssal plains) and the other seamounts area with all three 
having similar median ranges and means. The MPS area has 
the highest cobalt values, with a median range of 0.7 to 0.8 
wt-pct and a mean of 0.76 wt-pct. Figure 18 provides 
histograms that show cobalt distribution in each of the four 
areas. 

Cobalt occurs in Pacific nodules in both the manganese 
and iron phases. Its occurrence is dependent on the 
oxidation of cobalt to either Co^^ or Co^". In the MPS area, 
oxidation to Co^" is one probable explanation of high cobalt 
values, whereas in the deep ocean the oxidation potential 
may be insufficient to oxidize Co^' to Co^". Some cobalt in 
nodules can also be attributed to volcanic seamounts. Cobalt 
in the Co^' state has an ionic radius similar to Mn^-, whereas 
Co'' has an ionic radius very close to that of Mn"' and 
substitutes for Mn"' in vernadite (13, 100). 

Cobalt in CC-Zone area nodules has a slight positive 
correlation (table 19) with Fe, Pb, and Ti, and a slight 
negative correlation with Cd. In the MPS area, cobalt is 
positively correlated with Ba, Mg, Mn, Ni, Pb, Sr, Ti, and Zr. 
and negatively correlated with Al, Ca, K, Na, and Si. In the 
other abyssal plains area, cobalt has a slight positive 
correlation with Fe and Sr, and a slight negative correlation 
with Al, Cd, and Si. In the other seamounts area, cobalt is 
positively correlated with Ti and Pb, and has a slight positive 
correlation with Ni. Cobalt in this area has a slight negative 
correlation with Cd and Si. 

Zinc 

Zinc concentrations in Pacific nodules vary from <0.05 to 
0.95 wt-pct, with a median value of 0.05 to 0.15 wt-pct and a 
weighted mean of 0.11 wt-pct based on 3,097 sample 
analyses. The median value for CC-Zone area nodules is 
0.10 to 0.15 wt-pct with a mean of 0.14 wt-pct. Zinc values 
are highest in CC-Zone nodules; approximately a factor of 
two higher than in the other three areas. The median range 
for the other three areas is 0.05 to 0.10 wt-pct with a mean 
range of 0.07 to 0.09 wt-pct; the lower values occur in the 
seamount areas. Figure 19 provides histograms that show 
zinc distribution in each of the four areas. 

Zinc appears to occur in Pacific nodules as a substitute in 
the manganese mineral structure similar to copper and 
nickel. No zinc minerals have been identified in Pacific 
nodules. The zinc ionic radius is similar to Mn^ and would 
allow a direct substitution. 

Zinc in CC-Zone area nodules is positively correlated 



(table 19) with Cu, Mn, and Ni, and negatively correlated with 
Fe and Zr, with only a slight negative correlation with Pb and 
Ti. In the MPS area, zinc is positively correlated with Ba, Mn, 
Na, Ni, and V, and negatively correlated with Mg, Ti, and Zr. 
In the other abyssal plains area, zinc is positively correlated 
with Cu, Mn, and Ni, and negatively correlated with Al. In the 
other seamounts area, zinc is positively correlated with Cd, 
Cu, and Ni, and negatively correlated with Na. 

Vanadium 

Vanadium concentrations in Pacific nodules vary from 
<0.005 to 0.300 wt-pct, with a median value of 0.040 to 
0.080 wt-pct and a weighted mean of 0.050 wt-pct based on 
507 sample analyses. The median value for CC-Zone area 
nodules is 0.04 to 0.05 wt-pct with a mean of 0.047 wt-pct. 
The CC-Zone area and other abyssal plains area have 
somewhat lower median and mean values than the two 
seamount areas by about a factor of 1 .5 to 2.0. Figure 20 
provides histograms that show vanadium distribution for 
each of the four areas. 

Vanadium appears to be another of the many elements 
that occur with manganese and may possibly substitute for 
Mn'* or fill the large tunnels in the manganese mineral 
structure as oxides. Correlation coefficient data (table 19) 
indicate a tendency for vanadium to occur with Mn, Cu, and 
Ni, all of which have been shown to substitute for manganese 
in the manganese mineral structure. 

Vanadium in CC-Zone area nodules correlates with Ca, 
Cu, Mn, and Ni, and negatively with Al and Na. In the MPS 
area, vanadium correlates positively with K, Na, and Zn, and 
negatively with Mo, Pb, and Ti. In the other abyssal plains 
area, vanadium correlates positively with Fe and Mo and 
negatively with Si. In the other seamounts area, vanadium 
correlates positively with Al, Cu, Fe, K, and Ti, and negatively 
with Ba and Ca. Vanadium data for the seamounts areas are 
very limited; therefore, correlation coefficients may not 
accurately reflect the actual correlation of vanadium to other 
elements. 

Molybdenum 

Molybdenum concentrations in Pacific nodules vary from 
<0.005 to 0.150 wt-pct, with a median value of 0.03 to 0.06 
wt-pct and a weighted mean of 0.04 wt-pct based on 1,157 
sample analyses. The median value for CC-Zone area 
nodules is 0.05 to 0.06 wt-pct with a mean value of 0.05 
wt-pct. Molybdenum concentrations appear to be somewhat 
uniform throughout all four areas with only a slightly lower 
mean for the other abyssal plains area. Figure 21 provides 
histograms that show molybdenum distribution for each of 
the four areas. 

Moiyboenum appears to occur in a manner similar to that 
of Cu and Ni; that is, as a substitute in the manganese 
mineral structure. No molybdenum minerals have been 
identified in Pacific nodules. The ionic radius of molybdenum 
in oxidation states 4 and 6 is similar to Mn"*, and therefore it 
may be a substitute for Mn" or it may be contained in the 
smaller tunnel structure of the manganese minerals. 

Molybdenum in CC-Zone area nodules is positively 
correlated (table 19) with Cd, Cu, Mn, and Ni, and negatively 
correlated with Fe. In the MPS area, molybdenum is 
positively correlated with Mn, Na, and Ni, and negatively 
correlated with Al and V. In the other abyssal plains area, 
molybdenum is positively correlated with Cd, Mn, Ni, and V, 
and negatively correlated with Al and Si. In the other 
seamounts area, molybdenum is positively correlated with 
Na and Pb and has no negative correlation. Molybdenum 
data in the two seamounts areas are limited; therefore, 
correlation coefficients may not accurately reflect the actual 
correlation of molybdenum to other elements. 



24 



936 


- 




1 1 1 


832 


- 




- 


UJ 728 








O 








fi 








IT 








IT 








3 624 


^ 




- 


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O 








u. 








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> 520 


^ 






- 


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y 




















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g 416 
11. 


h 






- 










312 


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- 


208 


- 








- 


104 


_ 










1 1 1 



0.3 



0.6 0.9 

Co-CC ZONE, pet 



1.2 



1.5 



32 



28 - 



24 



20 



16 



12 



0.3 0.6 0.9 1.2 

Co-MID-PACIFIC SEAMOUNTS, pet 



1.5 



567 


- 




1 1 1 1 


504 


- 






T 


441 


- 






- 


OF OCCURRENCE 

Cfl 00 


^- 








- 


FREQUENCY 












- 










189 














126 


- 










- 


63 


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Ik-,, — , . 



72 



63 



54 



45 



36 



27 



18 



^ m 



1.5 



0.3 0.6 0.9 1.2 

Co-OTHER ABYSSAL, pet 

Figure 18 Cobalt frequency distribution by environment for Pacific manganese nodules. 



0.3 0.6 0.9 1.2 

Co-OTHER SEAMOUNTS, pet 



1.5 



25 



800 





0.15 0.30 0.45 0.60 0.75 0.90 1.05 

Zn-CC ZONE, pet 



0.15 0.30 0.45 0.60 0.75 0.90 1.05 

Zn-MID-PACIFIC SEAMOUNTS, pet 



fbu 


1 — 1 


— 1 1 r- 1 1 1 


684 






" 


608 


- 




- 


532 


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OCCURRENCE 


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fe 380 


- 




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FREQUENCY 


- 




- 


228 


- 






- 


152 


- 






- 


76 


- 








— 1 



108 


- 


— 1 


1 1 1 1 ' 1 


96 


- 




- 


84 


- 




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72 


- 




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60 


- 




- 


48 


^ 




- 


36 


- 




- 


24 


- 




- 


12 


- 






n ^ , ^ , , , 



0.15 0.30 0.45 0.60 0.75 0.90 1.05 0.15 0.30 0.45 0.60 0.75 0.90 1.05 

Zn-OTHER ABYSSAL, pel Zn-OTHER SEAMOUNTS, pel 

Figure 19. — Zinc frequency distribution by environment for Pacific manganese nodules. 



26 





500 1,000 1,500 2,000 2,500 

V-CC ZONE, ppm 



500 1,000 1,500 2,000 2,500 

V-MID-PACIFIC SEAMOUNTS, ppm 



90 



81 - 



72 - 



63 



54 



O 
O 
O 

u. 45 
O 

>- 
U 

I 36 



27 



18 



\h 



n-n 



500 



1,000 1,500 2,000 2,500 



O 
O 
O 
u. 4 



1 I I 



1 - - 



500 



1,000 



1,500 2,000 2,500 



V-OTHER ABYSSAL, ppm V-OTHER SEAMOUNTS, ppm 

Figure 20. — Vanadium frequency distribution by environment for Pacific manganese nodules. 



27 





54 


1 




1 1 




48 


- 






~ 




42 


- 












_ 


UJ 






o 


















z 


















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cr 


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- 












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- 




12 


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- 




















- 


























1 1 



0.03 0.06 0.09 0.12 

Mo-CC ZONE, pet 



0.15 



14 



12 



10 



2 - 



_L_ 



0.03 0.06 0.09 0.12 0.15 

Mo-MID-PACIFIC SEAMOUNTS, pet 





180 


- 




1 1 1 




160 


- 






- 




140 


- 






_ 


m 
o 

z 

Ul 
IT 
CC 

=) 

o 
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o 

u. 
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120 
100 


- 








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o 

z 

UJ 

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UJ 

rr 


80 














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60 














- 




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1 1 




1 1 1 1 



0.03 



0.06 



0.09 



0.12 



0.15 



12 


- 










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- 


8 
















- 


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- 


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0.03 



0.06 



0.09 



0.12 



0.15 



Mo-OTHER ABYSSAL, pet Mo-OTHER SEAMOUNTS, pet 

Figure 21 — Molybdenum frequency distribution by environment tor Pacific manganese nodules. 



28 



Table 7. — Distribution of other major and minor elements in Pacific manganese nodules, by area, 

weight-percent 



Standard 
Area Range Median Mean, deviation Number of 

X of mean, samples 
ax 


Standard 
Range Median Mean, deviation Number of 
X of mean, samples 

crx 


Aluminum 


Sodium 


Clarion-Clipperton zone. 0.50-8 00 2.50-3.00 2.90 1.04 234 
Mid-Pacific seamounts. . <. 25- 6.00 .25- .75 1.20 .94 48 
Other abyssal plains, 

>3,000 m <.50-10.0 2.50-3.00 3.05 1.48 570 

Other seamounts, 

0,000 m <. 50- 7.00 1.00-1.50 1.70 1.11 79 


0.50 -6.75 2.00-2.25 2.79 1.72 106 
.50 -5.50 1.45-1.55 2.13 1.04 28 

<.25 -5.75 1.75-2.00 2.07 .78 297 

.25 -3.75 1.25-1.50 1.64 .76 37 


Calcium 


Strontium 


Clarion-Clipperton zone. <0.5 -18.0 1.5-2.0 1.7 0.8 872 
Mid-Pacific seamounts. . <.5 -25.0 2.0 - 2.5 4.2 3.9 91 
Other abyssal plains, 

>3,000 m <.5 -13.0 1.5-2.0 1.8 1.2 914 

Other seamounts, 

0,000 m <.5 -25.0 2.0-3.0 4.5 5.3 200 


<0.005-0.16 0.04-0.05 0.045 0.03 78 
<.005- .30 .14- .15 .13 .07 27 

<.005- .18 .07- .08 .08 .03 320 

<.005- .28 .13- .14 .135 .06 68 


Magnesium 


Titanium 


Clarion-Clipperton zone. <0. 25- 3.00 1.50-1.75 1.65 0.43 209 
Mid-Pacific seamounts. . .50-3.50 .75-1.25 1.41 .52 35 
Other abyssal plains, 

>3,000 m <. 25- 5.00 1.25-1.50 1.43 .69 361 

Other seamounts, 

<3,000 m <. 25- 4.25 1.50-1.75 1.79 .84 64 


0.10 -2.20 0.40-0.50 0.53 0.29 265 
.20 -2.20 1.10-1.20 1.12 .40 102 

<.05 -2.50 .60- .70 .78 .75 854 

<.05 -1.60 .40- .50 .47 .35 89 


Potassium 


Zirconium 


Clarion-Clipperton zone 0.20-3.00 0.80-0.90 1.01 0.53 123 
Mid-Pacific seamounts. . .10- .90 .30- .40 .41 16 35 
Other abyssal plains, 

>3,000 m 10- 3.00 .70- .80 .93 .60 335 

Other seamounts, 

0,000 m .10-1.60 .30- .40 .54 .47 66 


0.010-0.09 0.03-0.04 0.035 0.01 33 
<.005- .11 .07- .075 .06 .03 18 

<.005- .20 .05- .06 .06 .04 226 

<.005- .20 .04- .05 .05 .04 27 


Silicon 




Clarion-Clipperton zone. 1.0-25.0 6.0-6.5 7.6 2.91 339 
Mid-Pacific seamounts. . <. 50-15.0 2.0-3.0 3.6 3.03 45 
Other abyssal plains, 

>3,000 m <. 50-25.0 7.0 - 8.0 8.8 5.10 460 

Other seamounts, 

0,000 m <. 50-23.0 3.0 - 4.0 4.8 4.45 91 





General Observations 

CC-Zone area nodules contain the highest levels of Mn, Ni, 
Cu, and Zn and the lowest amounts of Fe and Co. Vanadium 
is slightly lower in the CC-Zone area than in other areas and 
molybdenum appears to be uniformly concentrated in all 
areas. The seamounts areas contain the highest levels of Fe 
and Co with a slight elevation of V, and they contain the 
lowest levels of Ni and Cu. The different environments 
encountered in the seamounts areas versus the abyssal 
areas may show the effect of oxidation and sediment types 
on the formation of Pacific nodules. Cobalt occurs with both 
the Fe and Mn phases, with higher Co and Fe values being 
observed in nodules formed in the more elevated sea floor 
areas (MPS and other seamounts areas). The majority of 
data in this section came from the work of Frazer {44, 48-50), 
Sorem {118), and Fewkes {42-43). 



Table 8. — Distribution of other major and minor 
elements in Pacific manganese nodules, compo- 
site, weight-percent 



Element Range 

Aluminum <0.25 -10.0 

Calcium < .05 -25.0 

Magnesium < .25 - 5.0 

Potassium .10-3.0 

Silicon <.50 -25.0 

Sodium <.25 - 6.75 

Strontium <.005- .300 

Titanium <.05 - 2.50 

Zirconium <.005- .20 



Range of 
medians' 



Weighted 
mean 



Number of 
samples 



0.25-3.0 


2.80 


931 


1 .50-3.0 


2.12 


2,077 


.75-1.75 


1.53 


669 


.30- .90 


.87 


559 


2.0 -8.0 


7.72 


935 


1.25-2.25 


2.20 


468 


.04- .15 


.083 


493 


.40-1.20 


.73 


1,310 


.03- .075 


.058 


304 



OTHER MAJOR AND 
MINOR ELEMENTS 

The major and minor elements discussed in this section 
are not of any present economic or environmental interest as 
applied to manganese nodule processing. The nine ele- 
ments, Al, Ca, Mg, K, Si, Na, Sr, Ti, and Zr, are presented in 
the same manner as those of economic interest, with data 
divided into the four geographic areas as shown in table 7. 
Possible mineral forms and compounds are presented as 
well as positive and negative interelement correlations (table 
19). Table 8 gives composite data for these elements from 
Pacific nodules. 



Aluminum 

Aluminum concentrations in Pacific nodules vary from 
<0.25 to 10.0 wrt-pct, with a median value of 0.25 to 3.00 
wt-pct and a weighted mean of 2.80 wt-pct based on 931 
sample analyses. The median value for CC-Zone area 
nodules is 2.5 to 3.0 wt-pct with a mean of 2.9 wt-pct. 
Nodules from the two abyssal plains areas contain about 
twice the amount of aluminum found in nodules from the two 
seamounts areas. The two seamount areas have a median 
range of 0.25 to 1 .5 wt-pct, with means around 1 .2 wt-pct for 
MPS area and 1.7 wt-pct for the other seamounts area. 
Figure 22 provides histograms that show aluminum distribu- 
tion in each of the four areas. 



29 



14U 















[-- 1 -1 


126 






- 


112 


- 




- 


98 


- 




- 


84 


- 




- 


70 


- 




- 


56 


- 




- 


42 


- 






- 


28 


- 








- 


14 


- 












- 













4 6 8 

AI-CC ZONE, pet 



10 



12 



27 



24 



18 



15 



12 



a. Q 



3 - 



r\. 



2 4 6 8 10 

AI-MID-PACIFIC SEAMOUNTS, pet 



12 



C\>\i 


1 1 1 1 1 


180 


- 




- 


160 


- 




- 


140 


- 






- 


CCURRENCE 

ro 

o 


- 








_ 


o 

u. 100 

O 


r 




FREQUENCY 

00 

o 


- 








- 


60 


- 








- 


40 












- 


20 


















■■I 1 



12 



JU 

27 


- 


T T 


1 1 1 


24 


- 


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- 


21 


- 








- 


18 


- 








- 


15 


- 








- 


12 


- 








- 


9 










- 


6 


- 








- 


3 










1 


1 1 , 



10 



12 



AI-OTHER ABYSSAL, pet AI-OTHER SEAMOUNTS, pet 

Figure 22 — Aluminum frequency distribution by environment for Pacific manganese nodules. 



30 



Aluminum occurs primarily as an aluminum silicate in clay 
inclusions in Pacific nodules in the form of alkali and 
plagioclase feldspars. This is reflected in the correlation data 
(table 19) by positively correlating with K, Si, and, in some 
cases, Na. No correlation with Ca is observed except for a 
slight negative correlation in the other seamounts area. The 
most likely form is plagioclase, other feldspars, and clays. 

Aluminum in CC-Zone area nodules correlates positively 
with Ba, Cu, K, Na, and Si and negatively with Cd, Mg, Mn, 
Sr, and V. In the MPS area, aluminum is positively correlated 
with Cr, Mg, Ti, and Zr, and negatively correlated with Co, 
Cu, Mn, Mo, Na, and Ni. In the other abyssal plains area, 
aluminum is positively correlated with K and Si, and 
negatively correlated with Cd, Co, Mn, Mo, and Zn. In the 
other seamounts area, aluminum is positively correlated with 
Si, V, and Zr, and a slight negative correlation is observed 
with Ca, Cr, Mn, and Sr. 

Calcium 

Calcium concentrations in Pacific nodules vary from <0.5 
to 25.0 wt-pct, with a median value of 1 .5 to 3.0 wt-pct and a 
weighted mean of 2.1 wt-pct based on 2,077 sample 
analyses. The median value for CC-Zone area nodules is 1 .5 
to 2.0 wt-pct with a mean of 1 .7 wt-pct. Nodules from the two 
abyssal plains areas contain about one-half the calcium 
levels of nodules from the two seamounts areas. These two 
areas have a median range of 2.0 to 3.0 wt-pct with means 
between 4.2 and 4.5 wt-pct. Figure 23 provides histograms 
that show calcium distribution in each of the four areas. 

Calcium occurs in Pacific nodules in several possible 
forms. It can occur in some cases as calcite, apatite and/or in 
feldspars, and it correlates negatively in some areas with Fe 
and Mn. Calcium also is known to substitute in the 
manganese mineral structure to some degree. The multiform 
occurrence may be why the correlation coefficients (table 19) 
are not conclusive evidence for calcium association. 

Calcium in CC-Zone area nodules correlates positively 
with Cd, Sr, and V, and negatively with Ba. In the MPS area, 
calcium correlates positively with Sr and negatively with Cr, 
Co, Fe, and Mn. In the other abyssal plains area, calcium 
correlates positively with Mg and has no negative correlation. 
In the other seamounts area, calcium correlates positively 
with Cd and Sr, and negatively with Al, Fe, K, Na, Si, Ti, and 
V. 

Magnesium 

Magnesium concentrations in Pacific nodules vary from 
<0.25 to 5.0 wt-pct, with a median value of 0.75 to 1.75 
wt-pct and a weighted mean of 1.53 wt-pct based on 669 
sample analyses. The median value for CC-Zone area 
nodules is 1.5 to 1.75 wt-pct with a mean of 1.65 wt-pct. 
Magnesium concentrations are uniform in all four areas with 
only insignificant differences in median ranges and means. 
Figure 24 provides histograms that show magnesium 
distribution in each of the four areas. 

Magnesium occurs in Pacific nodules in several forms. 
Some of the magnesium content of nodules is a result of 
dissolved seawater salts. Magnesium also appears to occur 
in the manganese mineral structure based on its positive 
correlation (table 19) with Mn, Ni, and Cu in most areas. Its 
ionic radius is such that it could substitute in the same sites 
as Cu and Ni in the manganese crystal structure. 

Magnesium in CC-Zone area nodules correlates positively 
with Cu, Mn, Ni, and Sr, and negatively with Al, Fe, K, Na, 
and Ti. In the MPS area, magnesium is positively correlated 
with Al, Co, Cr, Ni, Pb, and Sr, and negatively correlated with 
Zn and Zr, In the other abyssal plains area, magnesium is 
positively correlated with Cd and Ca (slightly) and shows no 
negative correlation. In the other seamounts area, magne- 
sium is positively correlated with Ba, Cu, and Ni, and 
negatively correlated with Na and Sr. 



Potassium 

Potassium concentrations in Pacific nodules vary from 
0.10 to 3.0 wt-pct, with a median value of 0.30 to 0.90 wt-pct 
and a weighted mean of 0.87 wt-pct based on 559 sample 
analyses. The median value for CC-Zone area nodules is 
0.80 to 0.90 wt-pct with a mean of 1.01 wt-pct. The two 
abyssal plains areas contain about two times the amount of 
potassium found in the two seamounts areas. The median 
value for the seamounts areas is 0.30 to 0.40 wt-pct with 
means of 0.41 and 0.54 wt-pct. Figure 25 provides 
histograms that show potassium distribution in each of the 
four areas. 

The occurrence of potassium in Pacific nodules is in two 
forms: as dissolved sea salts that crystallize when the 
samples dry, probably as KCI (sylvite), and as plagioclase 
feldspars. Evidence for the latter is seen in the high 
correlation coefficients (table 19) for potassium with Al, Si, 
and Na. 

Potassium in CC-Zone area nodules is positively corre- 
lated with Al, Na, and Si, and negatively correlated with Cu, 
Mg, Mn, and Sr. In the MPS area, potassium is positively 
correlated with Na, Si, and V, and negatively correlated with 
Co and Pb. In the other abyssal plains area, potassium is 
positively correlated with Al and Si and negatively correlated 
with Cd, Fe, Mn, and Sr. In the other seamounts area, 
potassium is positively correlated with Cr and V and 
negatively correlated with Ca and Sr. 

Silicon 

Silicon concentrations in Pacific nodules vary from <0.50 
to 25 wt-pct, with a median value of 2.0 to 8.0 wt-pct and a 
weighted mean of 7.7 wt-pct based on 935 sample analyses. 
The median value for CC-Zone area nodules is 6.0 to 6.5 
wt-pct with a mean of 7.6 wt-pct. Silicon content in the two 
abyssal plains areas is a factor of two higher than for the two 
seamounts areas. The two seamounts areas have a median 
range of 2.0 to 4.0 wt-pct, with mean values of 3.6 wt-pct for 
the MPS area and 4.8 wt-pct for the other seamounts area. 
Figure 26 provides histograms that show silicon distribution 
in each of the four areas. 

Silicon occurs in Pacific nodules in two forms. It occurs as 
silicates in the feldspars and clays and as silica (Si02). 
Silicon in CC-Zone area nodules correlates positively (table 
19) with Al, K, and Na, and negatively with Cu, Mn, Ni, and 
Sr. In the MPS area, silicon correlates positively with Cr, K, 
Na, and Zr, and negatively with Co, Pb, and Sr. In the other 
abyssal plains area, silicon correlates positively with Al, Cr, 
and K, and negatively with Co, Mn, Mo, Ni, Sr, V, and Zr. In 
the other seamounts area, silicon is correlated positively with 
Al and negatively with Ba, Ca, Co, and Sr. 

Sodium 

Sodium concentrations in Pacific nodules vary from <0.25 
to 6.75 wt-pct, with a median value of 1 .25 to 2.25 wt-pct and 
a weighted mean of 2.20 wt-pct based on 468 sample 
analyses. The median value for CC-Zone area nodules is 2.0 
to 2.25 wt-pct with a mean value of 2.8 wt-pct. Sodium 
content of Pacific nodules from all four areas is similar with 
lower sodium values occurring in the two seamounts areas 
based on limited data in these areas. Figure 27 provides 
histograms that show sodium distribution in each of the four 
areas. 

Sodium occurs in Pacific nodules in several forms. It 
occurs as dissolved sea salts that crystallize upon drying. It 
can also occur in some feldspars in the plagioclase group. 
Sodium is also a constituent of the manganese mineral 
structure of todorokite but is generally replaced by other 
cations such as Cu^' and Ni^*, which are thought to stabilize 
the crystal structure of the todorokite. 

Sodium in CC-Zone area nodules is correlated positively 



31 




12 16 20 

Ca-CC ZONE, pet 




8 12 16 20 

Ca-MID-PACIFIC SEAMOUNTS, pet 




O 

u. 35 

O 



21 h 



MlTff^ n 



.^d^ 



8 12 16 20 

Ca-OTHER ABYSSAL, pet 



8 12 16 20 

Ca-OTHER SEAMOUNTS, pet 



Figure 23. — Calcium frequency distribution by environment for Pacific manganese nodules. 



(table 19) with Al, Ba, K, Si, and Ti, and negatively with Cd, 
Cu, Mg, Mn, Sr, and V. In the MPS area, sodium is correlated 
positively with Ba, K, Mo, Ni, Si, V, and Zn, and negatively 
with Al, Co, Cr, Pb, Sr, and Ti. In the other abyssal plains 
area, sodium is correlated positively with none of the other 
elements and negatively with Cd and Cr. In the other 
seamounts area, sodium is correlated positively with Mn and 
Mo and negatively with Ca, Cr, Mg, and Zn. 

Strontium 

Strontium concentrations in Pacific nodules vary from 
<0.005 to 0.300 wt-pct, with a median value of 0.04 to 0.15 



wt-pct and a weighted mean value of 0.083 wt-pct based on 
493 sample analyses. The median value for CC-Zone area 
nodules is 0.04 to 0.05 wt-pct with a mean value of 0.045 
wt-pct. Strontium values are lower by a factor of two to three 
in the two abyssal plains areas than in the two seamounts 
areas. The two seamounts areas have a median range of 
0.13 to 0.15 wt-pct with a mean of 0.135 wt-pct. Figure 28 
provides histograms that show strontium distribution in each 
of the four areas. 

Strontium substitutes for calcium in the manganese 
nodules. Strontium is positively correlated (table 19) with Ca 
and in some areas with Mn, Ni, and Cu. Calcium can be part 
of the manganese mineral structure and is replaced bv 



32 



63 



56 



49 



42 



35 



28 



£ 21 



90 



72 - 



63 



UJ 

S 54 



45 



36 



27 - 



18 - 



~1 — I 



2 3 

Mg-CC ZONE, pet 



l>n ^ , r^ 




12 3 4 

Mg-MID-PACIFIC SEAMOUNTS, pet 





1 




1 1 1 


14 






10 


- 


- 


8 
6 


— 


|— 1 


4 
2 


— 1 p 


—1 



012345 01234 

Mg-OTHER ABYSSAL, pet Mg-OTHER SEAMOUNTS, pet 

Figure 24. — Magnesium frequency distribution by environment for Pacific manganese nodules. 



33 



18 - 



15 



OliJ^Il 



54 I — 



42 



36 




24 



IB - 



ifDizfikif 




0.5 1.0 1.5 2.0 2.5 

K-MID-PACIFIC SEAMOUNTS, pet 



3.0 



18 

15 

12 

9 

6 

3 


- 

^ 






-1 




r-i 














1 I 1 — 














1 1 



0.5 



2.5 



3.0 



0.5 



1.0 



1.5 



2.0 



2.5 



1.0 1.5 2.0 

K-OTHER ABYSSAL, pet. K-OTHER SEAt\/10UNTS, pet. 

Figure 25. — Potassium frequency distribution by environment for Pacific manganese nodules. 



34 



H 50 




10 r r-i ' 



rmK. 



n 

12 16 20 

Si-CC ZONE, pet 



28 



32 - 



24 - 





1 ! 1 1 
—1 


1 h^ 



8 12 16 20 

Si-MID-PACIFIC SEAMOUNTS, pet 



28 



24 






1 1 1 I 1 1 1 

IZ 

z 

1 



24 



4 a 12 16 20 24 28 4 8 12 16 20 

Si-OTHER ABYSSAL, pet Si-OTHER SEAMOUNTS. pot 

Figure 26. — Silicon frequency distribution by environment for Pacific manganese nodules. 



28 



35 



-I 1 1 r- 



18 



12 



y 9 



n 



2 3 4 5 

Na-CC ZONE, pet 




2 3 4 5 

Na-OTHER ABYSSAL, pet 



I 

I I 1 



10 



1.5 3.0 4.5 6.0 7.5 9.0 10.5 

Na-MID-PACIFIC SEAMOUNTS, pet 



t 

_j I I L__l L_i I I 



2 3 4 5 

Na-OTHER SEAMOUNTS, pel 



Figure 27. — Sodium frequency distribution by environment for Pacific manganese nodules. 



36 




500 1,000 1,500 2,000 2,500 3,000 

Sr-CC ZONE, ppm 



500 1,000 1,500 2,000 2,500 3,000 

Sr-MID-PAORC SEAMOUNTS. ppm 



40 



35 - 



8 ^ 

u. 
O 
> 
O 20 



- 






r- 
















-' 










1 1 1 1 1 1 1 ■■■T 






500 1,000 1,500 2.000 2,500 3,000 500 1,000 1,500 2,000 2,500 3,000 

Sf-OTHER ABYSSAL, ppm Sr-OTHER SEAMOUNTTS. ppm 

Figure 28. — Strontium frequency distribution by environment for Pacific manganese nodules. 



37 



strontium to a certain extent. Strontium does not occur in the 
feldspars based on the high negative correlation with Al, K, 
and Si. 

Strontium in CC-Zone area nodules correlates positively 
with Ca, Cu, Mg, Mn, Ni, and Pb, and negatively with Al, K, 
Na, Si, and Ti. In the MPS area, strontium is positively 
correlated with Ca, Co, Mg, Mn, Pb, and Ti, and negatively 
correlated with Na, Si, and Zr. In the other abyssal plains 
area, strontium is correlated positively with Co, Fe, Pb, and 
Ti, and negatively with Cr, K, and Si. In the other seamounts 
area, strontium is correlated positively with Ba and Ca and 
negatively with Al, K, Mg, and Si. 

Titanium 

Titanium concentrations in Pacific nodules vary from 
<0.05 to 2.5 wt-pct, with a median value of 0.40 to 1.20 
wt-pct and a weighted mean of 0.73 wt-pct based on 1,310 
sample analyses. The median value for CC-Zone area 
nodules is 0.40 to 0.50 wt-pct with a mean value of 0.53 
wt-pct. Titanium values are similar in the CC-Zone area, in 
the other abyssal plains area, and in the other seamounts 
area. The MPS area titanium values are about twice the 
concentrations seen in the other areas, with a median value 
of 1.10 to 1.20 wt-pct and a mean of 1.12 wt-pct. Figure 29 
provides histograms that show titanium distribution in each of 
the four areas. 

Titanium in Pacific nodules appears to be associated with 
the iron phases present based on the positive correlation 
(table 19) obtained with Fe and Co and negative correlation 
with Mn, Cu, and Ni. The ionic radius of Ti"* is similar to that 
of Fe^ and may allow it to substitute for Fe. Titanium has 
also been observed in nodules as ilmenite, rutile, and 
anatase. 

Titanium in CC-Zone area nodules is correlated positively 
with Co, Fe, Na, Pb, and Zr, negatively correlated with Cu, 
Mg, Mn, and Ni, and slightly negative with Sr and Zn. In the 
MPS area, titanium correlated positively with Al, Co, Cr, Fe, 
Pb, Sr, and Zr, and negatively with Na, V, and Zn. In the other 
abyssal plains area, titanium is correlated positively with Fe 
and Sr and has no negative correlation. In the other 
seamounts area, titanium is correlated positively with Co, Fe, 
Pb, and V, and negatively with Ba, Ca, and Cr. The number 
of sample analyses in the two seamounts areas is limited; 
therefore, correlation coefficients may not reflect the actual 
correlation of titanium to other elements. 

Zirconium 

Zirconium concentrations in Pacific nodules vary from 
<0.005 to 0.20 wt-pct, with a median value of 0.03 to 0.075 
wt-pct and a weighted mean of 0.058 wt-pct based on 304 
sample analyses. The median value for CC-Zone area 
nodules is 0.03 to 0.04 wt-pct with a mean value of 0.035 
wt-pct. The CC-Zone nodules have the lowest zirconium 



levels of the four areas; about one-half the levels of the other 
three areas. The median range for the other three areas is 
0.40 to 0.075 wt-pct with mean values from 0.054 to 0.062 
wt-pct. Figure 30 provides histograms that show zirconium 
distribution in each of the four areas. 

Zirconium appears to occur in Pacific nodules in associa- 
tion with the iron phases based on its strong negative 
correlations (table 19) with Mn, Cu, and Ni and positive 
correlations with Co and Fe. The ionic radius of Zr** is similar 
to that of Fe^* and may allow some substitution in the iron 
phases. 

Zirconium in CC-Zone area nodules is correlated positively 
with Fe and Ti and negatively with Cr, Cu, and Zn. In the MPS 
area, zirconium is correlated positively with Al, Co, Fe, Si, 
and Ti, slightly positive with Mn, and negatively with Ba, Cr, 
Cu, Mg, Pb, Sr, and Zn. In the other abyssal plains area, 
zirconium is correlated positively with Fe and negatively with 
Cr and Si. In the other seamounts area, zirconium is 
correlated positively with Al and Fe and exhibits no negative 
correlations. 

General Observations 

The two abyssal plains areas have the higher levels of Al, 
K, Si, and Na by about a factor of two over the two 
seamounts areas. In contrast, the two seamounts areas have 
higher Ca and Sr by the same factor. Magnesium, titanium, 
and zirconium values are relatively uniform with the CC-Zone 
area having the lowest zirconium values and the MPS area 
having the highest titanium values. 



ELEMENTS OF 

ENVIRONMENTAL 

INTEREST 

Any of the following eight elements — As, Ba, Cd, Cr, Pb, 
Hg, Se, Ag — when leached from wastes under conditions 
specified by the U.S. Environmental Protection Agency, will 
result in the waste being classified as a hazardous material, if 
their concentrations are greater than 100 times the National 
Drinking Water Standard. Data for Ba, Cd, Cr, and Pb are 
presented in table 9, by area, as in the previous sections. 
Data for the remaining elements (As, Hg, Se, and Ag), along 
with the other four listed in table 9, are presented in table 10 
as a composite for Pacific Ocean nodules. Correlation 
coefficients are given in table 19. These data are taken from 
the Sediment Data Bank (44, 48-50) as well as from Toth 
(123), Harhs (67), and from analytical studies sponsored by 
the Bureau of Mines. 

Arsenic 

Arsenic concentrations in Pacific nodules vary from 20 to 
540 ppm, with a median value of 164 ppm and a mean value 



Table 9. — Distribution of elements of environmental interest in Pacific manganes nodules, by area 



Area 


Range 


. . ^ Standard de- 
Median ^^.^"- viation of 
** mean, nx 


Number 

of 
samples 


Range 


Median ^f^ 


Standard de- 
viation of 
mean, ax 


Number 

of 
samples 






Barium, wt-pct 








Chromium, 


ppm 




Clarion-Clipperton zone 

Mid-Pacific seamounts 


<0.01 - 0.76 
.04 - .68 
<0.005- 0.800 
0.06 - 0.80 


0.20- 0.22 0.28 
.18- .20 .30 
.14- ,16 .20 
.32- .34 .37 


ND 

0.27 

18 

.33 


213 
39 

499 
59 


1- 150 
1- 40 
1- 150 
1- 130 


15- 20 27 
10- 20 58 
15-20 25 
30- 40 60 


ND 

147 

38 

129 


107 
22 


Other abyssal plains, >3,000 m . 
Other seamounts, <3,000 m 


227 
38 






Cadmium, ppm 






Lead, ppm 


Clarion-Clipperton zone 

Mid-Pacific seamounts 


1 -35 
1 -25 
1 -35 
1 -35 


10 -15 123 
5 -10 8.3 
5 -10 10.7 
5 -10 10.2 


ND 
7.6 
7.1 
8.2 


127 
15 

133 
23 


50-1,800 

100-4,700 

50-3,000 

50-3,000 


400- 500 450 
1,700-1,800 1,860 

700- 800 820 
1,000-1,100 1,030 


190 
950 
710 
770 


921 
105 


Other abyssal plains, >3,000 m , 
Other seamounts, < 3,000 m 


1,185 
206 


ND Not determined. 



















38 



72 



64 



56 



48 



8 



1 


1 1 1 1 

11 I— 1 r— 1 n 



32-1— — 1 



24 - 



0.4 0.8 1.2 1.6 2.0 2.4 

Ti-CC ZONE, pet 
120 



108 



98 



84 



72 



60 



48 



36 - 



24 



12 







0.4 0.8 1.2 1.6 2.0 2.4 

Ti-MID-PACIRC SEAMOl^fTS, pet 



16 



14 



12 



10 - 



o 

8 

>- 

o 



-I 1 1 1 r 



0.4 0.8 



1.2 



1.6 



2.0 2.4 



0.4 O.B 1.2 1.6 2.0 2.4 

Ti-OTHER ABYSSAL, pet TI-OTHER SEAMOUNTS, pet 

Figure 29 Titanium frequency distribution by environment for Pacific manganese nodules. 



39 



10 


1 


1 1 1 1 1 


16 
14 


- 


- 


12 
10 


- 


- 


6 


- 


- 


A 


- 


- 


2 


- 


- 




— 


1 1 J 



Hi 2 

o 






300 600 900 1,200 1,500 1,800 2,100 

Zr-CC ZONE, ppm 



300 600 900 1,200 1,500 1,800 2,100 

Zr-MID-PACIFIC SEAMOUNTS, ppm 



36 



32 - 



28 - 



24 



20 



"T" 



1 



1-1 l-l 



300 600 900 1,200 1,500 1,800 2,100 

Zr-OTHER ABYSSAL , ppm 



6 - 






300 600 900 1,200 1,500 1,800 2,100 

Zr-OTHER SEAMOUNTS, ppm 



Figure 30. — Zirconium frequency distribution by environment for Pacific manganese nodules. 



40 



Table 10. — Distribution of elements of environ- 
mental interest in Pacific manganese nodules, 
composite 



Element 


Range 


Range of 
medians 


Weighted 
mean 


Number of 
samples 


Arsenic .... ppm 


20-540 


164 


159 


122 


Barium . . wt-pct 


. <0.005-0.800 


0.140-O.340 


0.24 


810 


Cadmium . . ppm 


1.0-35 


5-15 


11 


298 


Chromium . ppm 


1.0-150 


10-40 


31 


394 


Lead ppm 


50-^,700 


400-1 ,800 


742 


2,417 


Mercury . . . ppm 


0.002-0.78 


0.085 


0.15 


68 


Selenium . . ppm 


30-77 


53 


52 


56 


Silver ppm 


0.001-0.68 


0.039 


0.10 


56 



of 159 ppm based on 118 sample analyses. Arsenic 
concentrations are generally lower in the CC-Zone area and 
higher in the seamounts area. The highest arsenic values 
appear in the other abyssal areas. Figure 31 is a histogram 
for Pacific nodules showing arsenic distribution. 

Arsenic occurs in Pacific nodules in association with iron 
and may be part of the iron phase structure. Arsenic is 
probably oxidized to the As^* state in nodules. Arsenic is 
correlated positively with Fe, Co, and Pb, with the strongest 
correlation occurring in CC-Zone area nodules. 

20 



16 



12 



4 - 






50 



100 150 200 250 300 350 400 450 



As-PACIFIC OCEAN, ppm 

Figure 31 . — Arsenic frequency distribution for 
Pacific manganese nodules. 



Barium 

Barium concentrations in Pacific nodules vary from <0.005 
to 0.800 wt-pct, with a median value of 0.14 to 0.34 wt-pct 
and a weighted mean of 0.24 wt-pct based on 810 sample 
analyses. The median value for CC-Zone area nodules is 
0.20 to 0.22 wt-pct with a mean value of 0.28 wt-pct. The two 
abyssal plains areas have lower barium values than the two 
seamounts areas. Figure 32 provides histograms that shows 
barium distribution in each of the four areas. 

Barium in Pacific nodules occurs as barite and also 
substitutes into the structure of certain manganese minerals. 
Barium in CC-Zone area nodules is correlated positively 
(table 19) with Al and Na and negatively with Ca. Some 
indications are that barium is positively correlated in 
CC-Zone area nodules with Mn, Ni, Cu, and Zn based on a 
selected analysis of 22 samples in this area. In the MPS 
area, barium is correlated positively with Co, Na, Pb, and Zn, 
and negatively with Fe and Zr. In the other abyssal plains 
area, barium is positively correlated only with Cd. In the other 
seamounts area, barium is positively correlated with Cd, Mg, 
Mn, and Sr, and negatively with Fe, Si, Ti, and V. 



Cadmium 

Cadmium concentrations in Pacific nodules vary from 1 to 
35 ppm, with a range of median values for the different areas 
of 5 to 1 5 ppm and a mean value of 1 1 ppm based on 298 
sample analyses. The median value for CC-Zone area 
nodules is 10 to 15 ppm with a mean of 12 ppm. Cadmium is 
higher for CC-Zone area nodules than for other areas but 
only marginally. Figure 33 provides histograms that show 
cadmium distribution in each of the four areas. 

Cadmium levels in nodules are enriched over the sediment 
levels in deep sea clays. Cadmium appears to be part of the 
manganese mineral structure and may substitute in or fill the 
tunnels of these structures. 

Cadmium in CC-Zone area nodules is correlated positively 
(table 19) with Ca, Cu, Mn, Mo, and Ni, and negatively with 
Al, Co, Fe, Na, and Pb. In the MPS area, cadmium does not 
correlate with any element based on a limited number of 
sample analyses. In the other abyssal plains area, cadmium 
is correlated positively with Ba, Cu, Mg, Mn, Mo, and Ni, and 
negatively with Al, Co, Fe, K, Na, and Pb. In the other 
seamounts area, cadmium is correlated positively with Ba, 
Ca, Cu, Ni, and Zn, and negatively with Co, Cr, Mn, and Pb. 



Chromium 

Chromium concentrations in Pacific nodules vary from 1 to 
150 ppm, with a median value of 10 to 40 ppm and a 
weighted mean of 31 ppm based on 394 sample analyses. 
The median value for CC-Zone area nodules is 15 to 20 ppm 
with a mean value of 27 ppm. The CC-Zone and other 
abyssal plains areas contain the lower chromium values by 
about a factor of two compared with the two seamounts 
areas. The medians, however, show that all areas are similar 
with some increased chromium levels in the other seamounts 
area. Figure 34 provides histograms that show chromium 
distribution in each of the four areas. 

Chromium occurs in Pacific nodules associated with the 
gangue minerals, possibly the silicates, because of its 
tendency to be positively correlated (table 19) with Si. 
Chromium content in nodules is considerably lower than in 
deep-sea clays or oceanic basalts and is generally associ- 
ated in nodules with the entrapped sediment or other 
extraneous phases. 

Chromium in CC-Zone area nodules is correlated positive- 
ly with no elements and negatively with Zr. In the MPS area, 
chromium is correlated positively with Al, Cu, Mg, Ni, Si, and 
Ti, and negatively with Ca, Na, and Zr based on a very limited 
number of sample analyses. In the other abyssal plains area, 
chromium is correlated positively with Si and negatively with 
Na, Sr, and Zr. In the other seamounts area, chromium is 
correlated positively with Fe and K and negatively with Al, 
Cd, Na, and Ti based on a limited number of sample 
analyses. 

Lead 

Lead concentrations in Pacific nodules vary from 50 to 
4,700 ppm, with a range of median values for the different 
areas in the Pacific of 400 to 1 ,800 ppm and a weighted 
mean of 742 ppm based on 2,417 sample analyses. The 
median value for CC-Zone area nodules is 400 to 500 ppm 
with a mean of 450 ppm. This area contains the lowest lead 
levels corresponding to the low iron levels in this area. The 
other areas have two to three times this level of lead as 
median and mean values. The highest values occur in the 
MPS area with a median value of 1 ,700 to 1 ,800 ppm and 
mean of 1 ,860 ppm. Figure 35 provides histograms that show 
lead distribution in each of the four areas. 

Lead is closely associated with iron in Pacific nodules, 
based on high correlations (table 1 9) for these two elements, 
and probably occurs in the amorphous iron phase. Lead in 
CC-Zone area nodules is correlated positively with Co, Fe, 



41 



26 
24 
22 
20 

18 



8 

u. 
O 
>- 12 

o 



10 



54 



36 - 



O 30 

U 

O 

u. 

O 

U 24 - 



£ 18 



12 



ium 



.12 .24 .36 .48 .60 .72 .84 

Ba-CC ZONE, wt-pct 



"T" 



miwyw] n 



.12 



.24 



.36 



.48 



.60 



.72 



.12 .24 .36 .48 .60 .72 

Ba-UID-PACIFIC SEAMOUNTS, wt-pct 



.84 






.12 



.24 



.72 



.84 



Ba-OTHER ABYSSAL, wt-pct Ba-OTHER SEAMOUNTS. wt-pct 

Figure 32. — Barium frequency distribution by environment for Pacific manganese nodules. 



42 



42 



10 20 30 

Cd-CC ZONE, ppm 





M 


1 1 1 




48 


- 




- 




42 


- 




- 


1 


36 

30 


- 




- 


fe 
















>- 
o 


24 








~ 


lU 

u. 






18 












12 


- 










- 




6 


- 












- 










1 



10 20 30 

Cd-OTHER ABYSSAL, ppm 



40 





"! 




1 


" 






5 - 




1 

j 
1 


UJ 

o 

z 

o 
o 
o 


4 ^ 
3 - 








^ 


o 






>- 
o 

o 










j 

I 


Li. 


2 • 

i 

iL 








1 



10 20 30 

Cd-MID-PACIFIC SEAMOUNTS, ppm 



40 



T 1 



10 20 30 

Cd-OTHER SEAMOUNTS. ppm 



40 



Figure 33. — Cadmium frequency distribution by environment for Pacific manganese nodules. 



43 




X 60 90 120 150 

Cr-CC ZONE, ppm 




120 150 



o 
o 

8 

u. 4 
O 

>- 

o 

s 



3 - 






10 



6 - 



2 - 



30 60 90 120 

Cf-MID-PACIFIC SEAMOUNTS, ppm 



30 



60 



90 120 



150 






150 



Cr-OTHER ABYSSAL, ppm Cr-OTHER SEAMOUNTS, ppm 

Figure 34. — Chromium frequency distribution by environment for Pacific manganese nodules. 



44 




O.OS 0.10 0.15 0.20 

Pb-CC ZONE, pet 



0.2b 



0.30 





1 1 I ■ 1 1 


108 - |-| 


- 


96 - "1 


- 


84-1- 


- 


72 - 


_ 




ffl 


60 - 


- 


48 - 


- 


36 - 


- 




1 n 


24 = 


- 


12 - 


-1 




- -\Wkj] . 



0.08 



0.24 



0.32 



0.40 0.48 




0.08 0.18 0.24 0.32 0.40 

Pb-MID-PACIFIC SEAMOUNTS, pet 



0.48 



18 I — 




0.05 0.10 0.15 0.20 0.25 0.30 

Pb-OTHER ABYSSAL, pd Pb-OTHER SEAMOUNTS, pet 

Figure 35. — Lead frequency distribution by environment for Pacific manganese nodules. 



45 



Sr, and Ti, and negatively with Cd, Cu, and Zn. In the MPS 
area, lead is correlated positively with Ba, Co, Mg, Mn, Sr, 
and Ti, and negatively with K, Na, Si, V, and Zr. In the other 
abyssal plains area, lead is correlated positively with Fe and 
Sr and negatively with Cd and Cu. In the other seamounts 
area, lead is correlated positively with Co, Mo, and Ti, and 
negatively with Cd. 

Mercury 

Mercury concentrations in Pacific nodules vary from 0.002 
to 0.78 ppm, with a median value of 0.085 ppm and a mean 
of 0.15 ppm based on a limited 68 sample analyses. These 
very low levels are of little consequence with respect to 
environmental issues. Figure 36 is a histogram for Pacific 
nodules showing mercury distribution. 

Mercury occurs at levels equal to or less than the 
surrounding sediments. It most likely is associated in the iron 
structure as mercury is significantly correlated only with iron 
based on the very limited amount of data available. 

20 



16 - 



12 - 



8 - 



rip 



.05 .10 



.35 .40 



.45 



.15 .20 .25 .30 
Hg-PACIFIC OCEAN, ppm 

Figure 36 Mercury frequency distribution for 

Pacific manganese nodules. 

Selenium 

Selenium concentrations in Pacific nodules vary from 30 to 
77 ppm with a median value of 53 ppm and a mean of 52 ppm 
based on only 56 sample analyses obtained from Bureau of 
Mines analyses. Indications are that these values may be as 
much as a factor of 1 high based on limited information from 
other nodules that are under study. Therefore, these values 
may not be representative of the true levels in nodules and 
should be used with caution until more data become 
available. CC-Zone area nodules appear to have somewhat 
lower concentrations of selenium than other nodules. Further 
study is required to determine if these values are representa- 
tive of all Pacific nodules. Figure 37 is a histogram for Pacific 
nodules showing selenium distribution. Selenium does not 
appear to be correlated with any major or minor element. 

Silver 

Silver concentrations in Pacific nod'iles vary from 0.001 to 
0.68 ppm, with a median value of 0.039 ppm and a mean 
value of 0.10 ppm based on 56 sample analyses. Silver 
concentrations are equal to or less than silver concentrations 
of deep-sea clays. No interelement correlations are found for 
silver. Figure 38 is a histogram for Pacific nodules showing 
silver distribution. 



20 



16 



12 - 



10 20 30 40 50 60 70 80 

Se-PACIFIC OCEAN, ppm 

Figure 37. — Selenium frequency distribution for 
Pacific manganese nodules. 



28 



24 



20 



U 

Z 
lU 

oc 

5 16 

o 

o 

o 



4 - 



£H] 



f~l !~l FT 



.05 .10 .15 .20 .25 .30 .35 .40 .45 

Ag-PACIFIC OCEAN, ppm 

Figure 38. — Silver frequency distribution for 
Pacific manganese nodules. 



General Observations 

Nodules are enriched in As, Cd, Pb, and Se relative to their 
concentrations in deep-sea clays. The elements Ba, Cr, Hg, 
and Ag occur in Pacific nodules at levels similar to or less 
than corresponding levels of these elements reported for 
deep-sea clays. 

In Pacific nodules, Ba and Cd are correlated with the Mn 
phases, and As, Pb, and Hg are correlated with the Fe 
phases. Barium may also occur as barite in the gangue 
minerals. Chromium appears to be correlated with silicon and 
may occur with entrapped sediments. No correlations for 
selenium and silver were noted. 

The CC-Zone area and other abyssal plains areas contain 



46 



the lowest Cr, Pb, and Se levels and the highest levels of Ba 
and Cd. The highest lead values occur in the MPS area. 

Data tor As, Hg, be, and Ag are very limited; most of these 
data were generated for this report from selected nodule 
samples. Data for Ba, Cd, Cr, and Pb are more prevalent, 
and interpretations of these data are made with greater 
confidence. Based on the available information, the concen- 
trations of many of these elements are too low to warrant 
environmental interest. 

RARE-EARTH ELEMENTS 

The elements examined in this section are hafnium and all 
of the lanthanide series elements with the exception of 
promethium. For Pr, Dy, and Er, only limited sample analyses 
were available, and no histograms are provided. Figures 39 
through 50 are histograms for those elements with greater 
than 40 sample analyses. Data for these elements are 
presented for the composite of the Pacific nodules as they 



are too limited to present by area. Table 1 1 lists the elements 
by atomic number with concentration range, median, mean, 
and total number of samples. A majority of the data available 
for these elements is from analysis of nodules taken from the 
CC-Zone area. 




100 200 300 

U-PACFIC OCEAN, ppm 



400 



500 



Figure 39.— Lanthanum frequency distribution 
for Pacific manganese nodules. 



28 



24 



20 



16 



12 



4 - 



ri 



50 



100 150 200 250 300 350 



Nd-PACIFIC OCEAN, ppm 

Figure 41. — Neoaymium frequency distribution 
for Pacific manganese nodules. 



28 



24 



20 



16 - 



O 

>- 

y 12 1- 



mi 



n , n 



ifl 



24 



20 



s « 



12 



4 - 



n 



800 1,200 1,600 2,000 2,400 2,800 3,200 
Ce-PACIFIC OCEAN, ppm 



10 



20 30 40 50 60 70 



Figure 40. — Cerium frequency distribution for 
Pacific manganese nodules. 



Sm-PACIFIC OCEAN, ppm 

Figure 42. — Samarium frequency distribution 
for Pacific manganese nodules. 



47 



Table 11. — Rare-earth elements in Pacific 
manganese nodules, parts per million 



Element Range 

Lanthanum 66- 979 

Cerium 74-3,000 

Praseodymium . . . 26- 46 

Neodymium 60- 700 

Samarium 14- 141 

Europium 1- 27 

Gadolinium 14- 53 

Terbium 1- 11 

Dysprosium 22- 42 

Holmium 1- 8 

Erbium 11- 27 

Thulium 1- 9 

Ytterbium 8- 100 

Lutetium 1- 6 

Hafnium 3- 14 



Median 



Mean 



Number of 
samples 



130 


157 


151 


345 


530 


131 


34 


36 


8 


141 


158 


96 


32 


35 


115 


7 


9 


115 


33 


32 


57 


5 


5.4 


104 


32 


31 


18 


4 


4 


66 


19 


18 


18 


2 


2.3 


41 


17 


20 


171 


2 


1.8 


76 


5 


6 


96 



28 



24 



20 



16 



12 





1 




1 






1 1 


1 1 


- 


40 


- 






36 


- 








- 


32 


- 








- 


28 


- 










- 


24 


- 












_ 


20 


- 








16 
12 

a 


- 














- 


- 














- 


4 


I ^ 










1 1 


1 1 1 





26 



2 6 10 14 18 22 

Eu-PACIFIC OCEAN, ppm 

Figure 43. — Europium frequency distribution for 
Pacific manganese nodules. 



16 



10 



20 30 40 50 

Gd-PACIFIC OCEAN, ppm 



60 



Figure 44 — Gadolinium frequency distribution 
for Pacific manganese nodules. 



Tb-PACIFIC OCEAN, ppm 

Figure 45. — Terbium frequency distribution for 
Pacific manganese nodules. 



22 


1 




1 I 


20 


- 




- 


18 


- 




- 


16 


- 




- 


14 


- 






- 


12 


- 










- 


10 






- 


8 


- 










- 


6 


- 










- 


4 


- 












- 


2 








- 


r 






1 



2 4 6 8 

Ho-PACIFIC OCEAN, ppm 



Figure 46. — Holmium frequency distribution for 
Pacific manganese nodules. 



48 



20 
16 
12 






r 








8 
4 




J 


- 






, , r 



Tm-PACIFIC OCEAN, ppm 



Figure 47. — Thulium frequency distribution for 
Pacific manganese nodules. 



4U 

36 




I 1 


32 




- 


28 






- 


24 




- 


20 






- 


16 






- 


12 






- 


8 








- 


4 








- 




1 1 



2 4 6 

Lu-PACIFIC OCEAN, ppm 



Figure 49. — Lutetium frequency distribution for 
Pacific manganese nodules. 



52 




1 1 


1 




n " 




1 


1 


48 


- 






- 


44 


" 






- 


40 


- 




^ 




- 


36 












- 


32 


- 










- 


28 
24 


\- 










- 


20 












- 


16 


- 










- 


12 










1 


- 


4 


- 


' 












H 


' 


n 


1 — 1 



10 20 30 40 50 60 70 80 

Yb-PACIFIC OCEAN, ppm 

Figure 48. — Ytterbium frequency distribution for 
Pacific manganese nodules. 



24 


1 




1 1 1 1 "1 


22 


- 




" 


20 


- 






- 


18 


- 






- 


16 


- 






- 


14 


- 






- 


12 


- 






- 


10 
8 
6 
4 
2 


- 












- 


~ 






















1 1 



HI-PACIFIC OCEAN, ppm 

Figure 50. — Hafnium frequency distribution for 
Pacific manganese nodules. 



49 



The rare-earth values for Pacific nodules are primarily 
based on three publications, Glasby (60), Piper and 
Williamson (107), and Elderfield (41), plus data from the 
Sediment Data Bank (48). Rare-earth element content of 
nodules, with the exception of cerium, exhibits a decrease in 
rare-earth content relative to seawater content with increas- 
ing atomic number. Cerium shows a large enrichment 
relative to other rare-earth elements because of its oxidation 
to Ce"* in nodules and is associated primarily with the iron 
phase. Other rare-earth elements occur as oxides in both the 
iron and gangue phosphate phases. It has been reported that 
total rare-earth element content of Pacific nodules increases 
with increasing distance from land and is correlated with both 
the iron and manganese contents of nodules (127). A 
negative correlation of rare earths to silica content has also 
been observed. Rare-earth elements are incorporated in 
nodules mainly from seawater. Most variations of rare-earth 
content of nodules can be explained by dilution of the iron 
and manganese phases by silicate minerals. The rare earths 
are preferentially incorporated into nodules due to hydrolysis 
under oxidizing conditions (60). The rare-earth elements 
(exclusive of cerium) occur in two phases, a phosphate 
phase composed of fish debris and/or recrystallized biogenic 
apatite, and the hydrous iron oxide phase with chemisorbed 
phosphate. 



PRECIOUS-METAL- 
GROUP ELEMENTS 

The elements in this section are those elements that are 
classified as precious metals and/or platinum-group metals. 
Very limited sample analyses are available for Au, Ir, Pd, Pt, 
Re, and Ru (1, 45, 60, 112); therefore, no histograms are 
presented. No data are available for Os and Rh, and Ag is 
discussed with the elements of environmental interest. A 
summary of the elemental composition of Pacific nodules for 
the six elements is given in table 12. 

Gold values show a positive correlation with silica content, 
whereas iridium values show a negative correlation (60). 
Gold and palladium are depleted in Pacific nodules 
compared with deep sea sediments whereas iridium shows 
an enrichment in nodules relative to deep sea sediments. 
The ability for some of these elements to form stable anionic 
species (gold and rhenium) in seawater may explain their 
depletion in nodules. 

Table 12. — Precious-metal-group elements in 

Pacific manganese nodules, nanograms per 

gram 



Element 



Range 



Median 



Mean 



Number of 
samples 



Gold 


0.13- 3.9 


1.92 


1.93 


10 


Iridium 


0.2 


- 23.1 


4.3 


9.1 


11 


Palladium 


2.9 


- 9.2 


6.3 


6.2 


10 


Platinum 


<5 


-145 


110 


97 


5 


Rhenium 




<.2 


NAp 


NAp 


2 


Ruthenium 




18 


NAp 


NAp 


1 


NAp Not applicable. 




RADIC 
ELE 


►ACTIVE 


• 






MENTS 





Only limited data are available on the radioactive 
elements, with only Ra, Th, and U being reported. Over 250 
sample analyses are available for U and Th and nine values 
for Ra. Table 13 gives the Ra, Th and U data available for 
Pacific nodules. Figures 51 and 52 are histograms for 
thorium and uranium, respectively. Data for these elements 
were obtained from the Sediment Data Bank (48) and other 
sources (12, 81, 83-88, 96, 102). 



Table 13. — Radioactive elements in Pacific 
manganese nodules 



Element 



Range 



Median 



Mean 



Number of 
samples 



Radium . . pg/g . . 
Thorium . . ppm . 
Uranium, .ppm . 



1.0- 35.7 
5 -154 
1 - 68 



5.1 
21 
5 



8.5 
28 
6.8 



9 
283 
255 



110 



100 - 
90 
80 



o 

O 60 




160 180 



Th-PACIFIC OCEAN, ppm 

Figure 51. — Thorium frequency distribution for 
Pacific manganese nodules. 





BU 


1 1 1 1 1 


1 1 


1 




70 


- 


1 1 






- 


>- 
o 

z 

UJ 

oc 

(C 
3 

u 
o 

o 


60 
SO 


- 


1 










- 


u. 
O 


















> 

o 

z 

UJ 

o 

UJ 

a: 

U. 


40 
30 


- 












- 




20 


- 








-n 






- 




10 


— 
















- 






















1 ^r~ 


h^ , 1 1 , 


1 1 — 



12 16 20 24 28 

U-PACIFIC OCEAN, ppm 



Figure 52 Uranium frequency distribution for 

Pacific manganese nodules. 



50 



The uranium and thorium content of Pacific nodules (and 
other nodules) can be explained by coprecipitation from 
seawater with the iron phase. Uranium and thorium content 
of nodules is enriched over seawater and deep sea 
sediments. Their concentration is highest near the top 
surface interface with seawater and lowest at the bottom 
surface interface with the sediment. The interior of nodules 
has a concentration intermediate of the top and bottom 
surfaces. 

Several authors (81. 83, 85-87, 96) have suggested that a 
relationship exists between the thorium and uranium content 
of nodules and the water depth from which they are taken. 



OTHER TRACE 
ELEMENTS 

The 1 7 elements in this section for which data are available 
are Sb, Be, Bi, B, Cs, Ga, Ge, Li, Nb, Rb, Sc, Ta, Te, Tl, Sn, 
W, and Y. Table 14 gives the available information on these 
elements for Pacific nodules. Figures 53 through 60 are 
histograms for those elements where greater than 40 sample 
analyses are available. Data for these elements come from 
the Sediment Data Bank (48) as well as other sources. 

Table 14. — Other trace elements in Pacific 
manganese nodules, parts per million 



Element 



Range 



Median 



Mean 



Number of 
samples 



Antimony 14-72 36 37 

Beryllium 2-15 .2 4 

Bismuth 6-31 23 21 

Boron 17 -1,655 221 273 

Cesium <.50- 2.60 <.70 75 

Gallium 2-72 6 11 

Germanium 3-90 37 42 

Lithium 23 -1,055 100 160 

Niobium 6 - 150 80 74 

Rubidium 5-60 15 15 

Scandium 1-29 10 10 

Tantalum 2-20 11 11 

Tellurium 172 - 272 214 216 

Thallium 2-675 160 169 

Tin 2-450 80 108 

Tungsten 26 - 120 80 76 

Yttrium 17-950 111 133 



103 

29 

13 

94 

7 

39 

4 

25 

42 

43 

159 

4 

17 

141 

87 

7 

132 



24 



1 1 

, 1 1 




r 














- 



Of the 17 elements in this section, only eight have more 
than 40 sample analyses and only four have more than 100 
sample analyses. Antimony is thought to be associated with 
the manganese phase. These trace elements may occur with 
any of the three phases and/or be present as a result of 
seawater residue incorporation. 

Thallium merits special attention as the most enriched 
element in nodules when compared with deep sea sedi- 
ments. An inverse correlation is observed between thallium 
and silica content of nodules. Thallium as Th is stable in acid 
and alkaline environments whereas TP* is stable only at low 
pH and forms thallic hydroxide precipitate when TP" solutions 
are made basic. Thallium probably exists in nodules as thallic 
hydroxide, TI(0H)3. The nodule environment may oxidize the 
Tl* in sediments and precipitate thallium as the hydroxide 
{60). 



m 



100 200 300 400 500 600 700 800 900 

B-PACIFIC OCEAN, ppm 

Figure 54. — Boron frequency distribution for 
Pacific manganese nodules. 



" 14 



80 



140 



Sb-PACIFIC OCEAN, ppm 

Figure 53. — Antimony frequency distribution for 
Pacific manganese nodules. 



Nb-PACIFIC OCEAN, pprn 

Figure 55 — Niobium frequency distribution for 
Pacific manganese nodules. 



51 




20 30 



60 70 



Rb-PACIFIC OCEAN, ppm 

Figure 56 Rubidium frequency distribution for 

Pacific manganese nodules. 





45 


1 1 1 1 1 1 


1 






40 












tu 


35 


_ 










. 


o 

z 

UJ 
















u 


30 


" 










" 


o 

Li. 

o 


25 


- 












- 


> 












— 1 








z 

UJ 

o 


20 


- 














- 


IT 

Li. 


15 


- 














- 




10 


- 
















- 




5 


n 
















1 1 1 


1 1 


- 



Se-PACIFIC OCEAN, ppm 

Figure 57. — Scandium frequency distribution for 
Pacific manaanes*^ nodules. 




150 200 250 300 350 400 450 500 

T|. PACIFIC OCEAN, ppm 




50 100 150 200 250 300 350 400 450 500 



Sn-PACIFIC OCEAN, ppm 

Figure 59 — Tin frequency distribution for Pacil 
ic manganese nodules. 






100 150 200 250 300 

Y-PACIFIC OCEAN, ppm 



Figure 58 — Thallium frequency distribution for 
Pacific manganese nodules. 



Figure 60 Yttrium frequency distribution for 

Pacific manganese nodules. 



ANION-FORMING 
ELEMENTS 

The eight elements in this section occur almost exclusively 
as anions in the chemical structure of Pacific nodules. These 
elements are Br, C, CI, F, I, N, P, and S occurring as bromide, 
carbonate, chloride, fluoride, iodide, nitrate, pho&phate, and 
sulfate anions. The anions — chloride, fluoride, bromide, 
iodide — present in nodules are primarily the result of 
residues from evaporation of seawater. 

Carbon occurs as carbonate In the form of gangue 
minerals such as calcite and other carbonate minerals and as 
entrapped organic matter. 



52 



Phosphorus is present as phosphate minerals such as 
apatite and calcium phosphate and is associated with the 
iron phases. Shark teeth inclusions in nodules increase the 
phosphate level substantially. Phosphorite pellets (apatite) 
have been observed as nucleii and inclusions in manganese 
nodules. 

Sulfur as sulfate occurs in nodules in the form of barite 
(BaS04) and other sulfate minerals. The sulfide form is not 
very common in the oxidizing environment in which nodules 
are formed. 

Data for nitrogen as nitrate are limited; nitrate is 
undoubtedly a residue from seawater. Table 1 5 is a summary 
of the data available for these elements. 

Table 15. — Anion-f orming elements in Pacific 
manganese nodules, weight-percent 

Number of 
Range samples 



Element Form 

Bromine Br" 

Carbon CO3" 

Chlorine C[ 

Fluorine F" 

Iodine I 

Nitrogen NO3 

Phosphorus P20s 

Sulfur S04~ 



0.002-0.080 


7 


.30 -1.70 


22 


<.01 -1.10 


10 


<.01 - .05 


6 


<.01 - .25 


7 


<.01 - .18 


6 


<.01 -2.20 


158 


.07 -6.60 


24 



SUMMARY TABLES 

This section of the report contains summary tables for the 
21 major and minor elements for each of the four areas of the 
Pacific. Table 16 is the summary table for the CC-Zone area, 
the MPS area, the other abyssal plains area, and the other 
seamounts area. Table 1 7 gives the composite composition 
of all 74 elements discussed in this report. The mean values 
in table 1 7 for the 21 major and minor elements (including Ba, 
Cd, Cr, and Pb) are weighted averages based on the total 
number of analyses from each area. The median range for 
these elements is the lowest and highest median value for 
the four areas for each element. Table 1 8 is a list of those 
elements not included in this report owing to absence of data, 
exclusive of inert gases and transuranium elements. Table 
19 lists interelement correlation coefficients found for the 21 
major and minor elements from the CC-Zone area, the MPS 
area, the other abyssal plains area, and the other seamounts 
area. 



CROSS SECTION ANALYSIS 

The variation of elemental composition in a nodule cross 
section is shown in figures 61 through 65 and table 20. Figure 
61 shows a cross section of a nodule and the analysis points. 



Table 16. — Summary of major, minor, and some trace elements in Pacific manganese nodules, by 

area 



Element 



Range 



Median 



Mean 



Number 

of 
samples 



Range 



Median 



Mean 



Number 

of 
samples 



Clarion-Clipperton zone 



Other abyssal plains, >3,000 m 



Aluminum wt-pct . 

Barium wt-pct . 

Cadmium ppm . 

Calcium wt-pct. 

Chromium ppm . 

Cobalt wt-pct . 

Copper wt-pct . 

Iron wt-pct . 

Lead wt-pct . 

Magnesium wt-pct . 

Manganese wt-pct . 

Molybdenum wt-pct. 

Nickel wt-pct . 

Potassium wt-pct . 

Silicon wt-pct . 

Sodium wt-pct . 

Strontium wt-pct . 

Titanium wt-pct . 

Vanadium wt-pct . 

Zinc wt-pct . 

Zirconium wt-pct . 

Aluminum wt-pct . 

Barium wt-pct . 

Cadmium ppm . 

Calcium wt-pct. 

Chromium ppm . 

Cobalt wt-pct . 

Copper wt-pct . 

Iron wt-pct . 

Lead wt-pct . 

Magnesium wt-pct . 

Manganese wt-pct . 

Molybdenum wt-pct . 

Nickel wt-pct . 

Potassium wt-pct . 

Silicon wt-pct . 

Sodium wt-pct . 

Strontium wt-pct . 

Titanium wt-pct . 

Vanadium wt-pct . 

Zinc wt-pct . 

"Zirconium wt-pct . 



0.5-8.0 


2.5-3.0 


2.9 


234 


<0.5-10.0 


2.5-3.0 


3.0 


570 


<0.01-O.76 


0.20-0.22 


0.28 


213 


<0,005-0.80 


0.14-0.16 


0.20 


499 


1-35 


10-15 


12.3 


127 


1-35 


5-10 


10.7 


133 


<0.5-18.0 


1.5-2.0 


1.7 


872 


<0.5-13.0 


1.5-2.0 


1.8 


914 


1-150 


15-20 


27 


107 


1-150 


15-20 


25 


227 


<0.1-0.9 


0.20-0.30 


0.24 


1,925 


<0.1-1.4 


0.2-0.3 


0.24 


2,219 


0.1-2.0 


1.0-1.1 


1.02 


2,236 


<0.05-2.00 


0.30-0.40 


0.42 


2,282 


1-25 


6-7 


6.9 


2,215 


1-25 


12-13 


12.7 


2,325 


0.005-O.18 


0.040-0.050 


0.045 


921 


0.005-0.30 


0.07-0.08 


0.082 


1,185 


<0.25-3.0 


1.50-1.75 


1.65 


209 


<0.25-5.00 


1.25-1.50 


1.43 


361 


1-39 


26-27 


25.4 


2.227 


1-40 


18-19 


18.5 


2,354 


<0.005-0.12 


0.05-0.06 


0.052 


265 


<0.005-0.13 


0.03-0.04 


0.036 


746 


0.1-2.0 


1.3-1.4 


1.28 


2,237 


0.1-2.0 


0.50-0.60 


0.63 


2,334 


0.20-3.0 


0.80-0.90 


1.01 


123 


0.10-3.0 


0.70-0.80 


0.93 


335 


1.0-25.0 


6.0-6.5 


7.6 


339 


0.5-25.0 


7.0-8.0 


8.8 


460 


0.5O-6.75 


2.00-2.25 


2.79 


106 


<0.25-5.75 


1.75-2.00 


2.07 


297 


<0.005-0.16 


0.040-O.050 


0.045 


78 


<0.005-0.18 


0.07-0.08 


0.077 


320 


0.10-2.20 


0.40-0.50 


0.53 


265 


<0.05-2.50 


0.60-0.70 


0.78 


854 


<. 005-0.08 


0.040-0.050 


0.047 


70 


0.01-0.30 


0.04-0.05 


0.048 


370 


<0.05-0.95 


0.10-0.15 


0.14 


1,539 


<0.05-0.95 


0.05-0.10 


0.09 


1,285 


0.010-0.09 


0.030-0.040 


0.035 


33 


<0.005-0.20 


0.05-0.06 


0.062 


226 


Mid-Pacific seamounts 




Other seamounts, 


<3,000 m 





<0.25-6.00 

0.04-0.68 

1-25 

<0, 5-25.0 

1-40 

<0.1-2.5 

<0.01-1.00 

2-25 

0.01-0.47 

0.50-3.50 

1-40 

<0.005-0.11 

0.1-1.5 

0.10-0.90 

<0.5-15.0 

0.50-5.50 

<0.005-0.30 

0.20-2.20 

<0.005-0.30 

<0.05-0.25 

<0.005-0.110 



0.25-0.75 

0.18-0.20 

5-10 

2.0-2.5 

10-20 

0.7-0.8 

<0.05 

14.5-15.5 
0.17-0.18 
0.75-1.25 
20-21 
0.05-0.06 
0.40-0.50 
0.30-0.40 

2.0-3.0 
1.45-1.55 
0.14-0.15 
1.10-1.20 
0.07-0.08 
0.05-0.10 
0.070-0.075 



1.20 

0.30 

8.3 

4.2 

58 

0.76 

0.10 

14.7 
0.186 
1.41 
20.8 
0.05 
0.49 
0.41 

3.6 
2.13 
0.13 
1.12 

0.086 
0.07 

0.061 



48 
39 
15 
91 
22 
182 
176 

185 
105 

35 
183 

56 
188 

35 

45 
28 
27 
102 
29 
82 
18 



<0.5-7.0 

0.06-0.80 

1-35 

<0.5-25.0 

1-130 

<0.05-1.40 

<0.05-1.20 

1-25 

0.005-0.30 

<0.25-4.25 

1-40 

<0.005-0.15 

0.1-1.4 

0.10-1.60 

<0.5-23.0 

0.25-3.75 

<0.005-0.28 

<0.05-1.60 

<0.005-0.14 

<0.05-0.55 

<0.005-0.20 



1.0-1.5 

0.32-0.34 

5-10 

2.0-3.0 

30-^0 

0.20-0.30 

<0.05 

16-17 
0.10-0.11 
1.50-1.75 

16-17 

0.03-0.04 

0.3-0.4 

0.30-0.40 

3.0-4.0 
1.25-1.50 
0.13-0.14 
0.40-0.50 
0.06-0.07 
0.05-0.10 
0.04-0.05 



1.7 
0.37 
10.2 
4.5 
60 
0.31 
0.11 

15.6 
0.10 
1.79 
17.8 
0.05 
0.35 
0.54 

4.8 
1.64 

0.135 
0.47 

0.067 
0.07 

0.054 



79 

59 

23 

200 

38 

293 

304 

312 
206 

64 
315 

88 
315 

66 

91 
37 
68 
89 
38 
191 
27 



53 



Table 17. — Summary of elements in Pacific manganese nodules 



Element and 
atomic number 



Range 



Median Mean 



Number 

of 
samples 



Element and 
atomic number 



Range 



Median Mean 



Number 

of 
samples. 



Aluminum 13. 

Antimony 51 . 

Arsenic 33. 

Barium 56 . 

Beryllium 4. 

Bismutfi 83. 

Boron 5 . 



Bromine 35. 

Cadmium 48. 

Calcium 20. 

Carbon' 6 . 

Cerium 58 . 

Cesium 55. 

Cfilorine 17. 

Cfiromium 24. 

Cobalt 27. 

Copper 29. 

Dysprosium 66. 

Erbium 68. 

Europium 63. 

Fluorine 9 . 



Gadolinium 64. 

Gallium 31 . 

Germanium 32. 

Gold 79. 

Hafnium 72. 

Holmium 67. 

Iodine 53. 

Iridium 77. 

Iron 26 . 

Lantfianum 57 . 

Lead 82. 

Lithium ; 3 . 

Lutetium 71 . 

Magnesium ... .12. 

Manganese .... 25 . 
Mercury 80 . 



wt-pct 
..ppm 
..ppm 
wt-pct 
..ppm 
..ppm 
..ppm 

wt-pct 
..ppm 
wt-pct 
wt-pct 
..ppm 
..ppm 
wt-pct 

..ppm 
wt-pct 
wt-pct 
..ppm 
..ppm 
..ppm 
wt-pct 

..ppm 
..ppm 
..ppm 

• • ng-'g 

..ppm 
..ppm 
wt-pct 

• ■ ng/g 
wt-pct 
..ppm 
wt-pct 
..ppm 
..ppm 
wt-pct 

wt-pct 

• ■ ng/g 



<0.25-10.00 

14-72 

20-450 

<0.005-0.800 

2-15 

6-31 

17-1,655 

0.002-0.080 

1-35 

<0.05-25.00 

0.30-1.70 

74-3,000 

<0.5-2.6 

<0.01-1.10 

1-150 

<0.05-2.50 

<0.01-2.00 

22-42 

11-27 

1-27 

<0.01-0.05 

14-53 

2-72 

3-90 

0.13-3.90 

3-14 

1-8 

0.01-0.25 

0.2-23.1 

1-25 

66-979 

0.005-0.470 

23-1 ,055 

1-6 

<0.25-5.00 

1-40 
2-775 



0.25-2.00 2.80 

36 37 

164 159 

0.140-0.340 0.239 

2 4 

23 21 

221 273 

0.05 0.05 

5-15 11 

0.50-3.00 2.12 

0.19 0.18 

345 530 

<0.7 0.75 

0.86 0.07 

10-^0 31 

0.20-0.80 0.44 

<0.05-1.10 0.66 

32 31 

19 18 

7 9 

<0.01 0.013 



33 
6 

37 

1.92 

5 

4 



32 

11 

42 

1.93 

6 

4 



0.023 0.051 

4.3 9.1 

6-17 10.4 

130 157 

0.040-0.180 0.072 

100 160 

2 1.8 

0.75-1.75 1.53 



16-27 
85 



21.6 
152 



931 Molybdenum . . .42. 

103 Neodymium 60. 

122 Nickel 28. 

810 Niobium 41 . 

29 Nitrogen^ 7. 

13 Palladium 46, 

94 Phospfiorus^ . . .15. 



7 

298 

2,077 

22 

131 

7 

10 

394 

4,619 

4,998 

18 

8 

115 

6 

57 
39 

4 
10 
96 
66 

7 

11 

5,037 

151 

2,417 

25 

76 

669 



Platinum 78. 

Potassium 19. 

Praseodymium .59. 

Radium 88. 

Rhenium 75. 

Rubidium 37. 

Ruthenium 44. 

Samarium 62. 

Scandium 21 . 

Selenium 34. 

Silicon 14. 

Silver 47. 

Sodium 11 . 

Strontium 38. 

Sulfur^ 16. 

Tantalum 73. 

Tellurium 52. 

Terbium 65. 

Thallium 81 . 

Thorium 90. 

Thulium 69. 

Tin 50. 

Titanium 22. 

Tungsten 74. 

Uranium 92. 

Vanadium 23 . 

Ytterbium 70. 

Yttrium 39. 



5,079 Zinc 30. 

68 Zirconium 40. 



wt-pct 
..ppm 
wt-pct 
..ppm 
wt-pct 
• ■ ng/g 
wt-pct 

■ • ng/g 
wt-pct 

ppm 

pg/g 
ng/g 

ppm 

ng/g 

ppm 

ppm 

ppm 

wt-pct 

■ • ng/g 
wt-pct 
wt-pct 

wt-pct 
ppm 
ppm 
ppm 
ppm 
ppm 
ppm 

.ppm 
wt-pct 
.ppm 
.ppm 
wt-pct 
.ppm 
.ppm 

wt-pct 
wt-pct 



<0.005-0.150 

60-700 

0.10-2.00 

6-150 

<0.01-0.18 

2.9-9.2 

<0.01-2.2 

5-145 

0.10-3.00 

26-46 

1.0-35.7 

<0.2 

5-60 

18 

14-141 

1-29 

30-77 

<0. 5-25.0 

2-680 

<0. 25-6.75 

<0.005-0.300 

0.07-6.6 

2-20 

172-272 

1-11 

2-675 

5-154 

1-9 

2-450 

<0.05-2.20 

26-120 

1-68 

<0.005-0.300 

8-100 

17-950 

<0.05-1.00 
<0. 005-0.200 



0.030-0.060 0.041 

141 158 

0.30-1.40 0.89 

80 74 

0.04 0.056 

6.3 6.2 

0.21 0.23 



110 

0.30-0.90 

34 

5.1 

NAp 

15 



97 
0.87 

36 

8.5 
NAp 

15 



NAp NAp 



32 
10 
53 
2.0-8.0 
39 



35 
10 
52 
7.8 
101 



1.25-2.25 2. 20 
0.040-0.150 0.083 



0.4 

11 

214 

5 

160 

21 

2 



1.84 
11 
216 
5.4 
169 
28 
2.3 



80 108 

0.40-1.20 0.73 

80 76 

C fi ft 

0.040-0.080 0.051 

17 20 

111 133 

0.05-0.15 0.11 

0.040-0.075 0.058 



1,157 

96 

5,074 

42 

6 

10 

158 

5 
559 
8 
9 
2 
43 
1 

115 
159 

56 
935 

56 
468 
493 

24 
4 

17 
104 
141 
283 

41 

87 
1,310 
7 
255 
507 
171 
132 

3,097 
304 



NAp Not applicable. 'As CO3 . ^as NOa". ^As PsOj. ''As SO4 



Table 18. — Elements for which no data were found for Pacific manganese nodules (exclusive of 

inert gases and transuranium elements) 



Atomic number 

Actinium 89 

Astatine 85 

Francium 87 

Indium 49 

Osmium 76 



Atomic number 

Polonium 84 

Promethium 61 

Protactinium 91 

Rodium 45 

Technetium 43 



Table 19. — Interelement correlation coefficients for Pacific manganese nodules, by area 



Element Al 



Ba Ca Cd Co Cr Cu 



Fe 



K Mg Mn Mo Na 



Pb 



Sr 



Zn 



CLARION-CLIPPERTON ZONE 



Al 1 

Ba 34 

Ca * 

Cd -.49 

Co * 

Cr * 

Cu 41 

Fe * 

K 63 

Mg -.50 

Mn -.52 

Mo * 

Na 67 

Ni ♦ 

Pb * 

Si 53 

Sr -.50 

Tl * 

V -.30 

Zn * 

Zr * 



0.34 

1 

-.31 



.40 



-* 


-0.49 


* 


-0.31 


* 


it 


1 


.33 


■k 


.33 


1 


-O.30 


* 


-.30 


1 


* 


-* 


* 


* 


.42 


* 


* 


-.30 


.33 


* 


* 


* 


* 


* 


* 


* 


.31 


* 


♦ 


.45 


* 


♦ 


-.32 


* 


* 


.57 


* 


* 


-.44 


.40 


* 


* 


* 


.56 


* 


• 


♦ 


* 


.36 


.30 


* 


* 



■58 



0.41 


* 


0.63 


-0.50 


-0.52 


* 


0.67 


■k 


* 


0.53 


-0.50 


* 


-0.30 


* 


* 


* 


* 


* 


* 


* 


* 


.40 


•k 


* 


ir 


-* 


* 


* 


* 


* 


* 


* 


* 


* 


* 


* 


• 


-* 


it 


•k 


.56 


* 


.30 


* 


* 


.42 


-0.30 


* 


♦ 


.31 


0.45 


-.32 


0.57 


-0.44 


ir 


* 


* 


* 


♦ 


* 


* 


.33 


* 


* 


* 


* 


* 


* 


.40 


■k 


* 


0.36 


* 


* 


* 


* 


* 


* 


* 


* 


* 


* 


* 


* 


* 


* 


* 


* 


* 


-0.58 


1 


-.64 


-.37 


.63 


.67 


.39 


-.48 


.80 


-.37 


-.40 


.66 


-.59 


.30 


0.44 


-.54 


-.64 


1 


* 


-.41 


-.42 


-.30 


* 


-.59 


.54 


* 


* 


.57 


* 


-.49 


.74 


-.37 


* 


1 


-.51 


-.59 


* 


.69 


* 


* 


.40 


-.44 


* 


* 


* 




.63 


-.41 


-.51 


1 


.69 


• 


-.62 


.52 


* 


* 


.63 


-.34 


* 


* 




.67 


-.42 


-.59 


.69 


1 


.71 


-.43 


.75 


* 


-.57 


.50 


-.49 


.37 


.51 




.39 


-.30 


* 


* 


.71 


1 


• 


.63 


* 


* 


* 


* 


* 


* 




-.48 


* 


.69 


-.62 


-.43 


-* 


1 


* 


1^ 


.30 


-.78 


.36 


-.36 


* 




.80 


-.59 


* 


.52 


.75 


.63 


* 


1 


* 


-.41 


.30 


-.54 


.36 


.47 




-.37 


.54 


if 


* 


* 


* 


* 


* 


1 


♦ 


.49 


.44 


• 


-.30 




-.40 


* 


.40 


* 


-.57 


* 


.30 


-.41 


* 


1 


-.37 


* 


* 


♦ 




.66 


* 


-.44 


.63 


.50 


• 


-.78 


.30 


.49 


-.37 


1 


-.30 


* 


* 




-.59 


.57 


* 


-.34 


-.49 


* 


.36 


-.54 


.44 


* 


-.30 


1 


* 


-.30 


,42 


.30 


* 


* 


* 


.37 


* 


-.36 


.36 


* 


-* 


* 


* 


1 


* 


* 


.44 


-.49 


* 


* 


.51 


• 


* 


.47 


-.30 


* 


* 


-.30 


♦ 


1 


-.43 


-.54 


.74 


* 


* 


* 


* 


* 


* 


* 


* 


♦ 


.42 


-* 


-.43 


1 



■ No significant correlation found. Coefficients ---0.3 or • 0.3 are considered significant 



54 



Table 19. — Interelement correlation coefficients for Pacific manganese nodules, by area — Con. 



Element Al Ba Ca Cd Co Cr Cu Fe K Mg Mn Mo Na Ni Pb Si Sr Ti 

MID-PACIFIC SEAMOUNTS 

Al 1 * * * -0.31 0.74 -0.31 * * 0.44 -0.53 -0.34 -0.34 -0.35 * * * 0.31 

Ba * 1 * * .42 * * -0.45 * * * * .33 ♦ 0.44 * * * 

Ca * * 1 * -.31 -.41 * -.60 * * -.46 ***** 0.61 * 

Cd * * *1 * * * * * * * * * * * * * * 

Co -.31 .42 -.31 * 1 * * * -0.41 ,53 .47 * -.34 .30 .74 -0.61 .61 .46 

Cr 74 * -.41 * * 1 .31 * * .64 * * -.51 .33 * .40 * .59 

Cu -.31 ****.311 *********** 

Fe * —.45 -.60 ****1 ********* .46 

K * * * * -.41 * * * 1 * * * .52 * -.32 .52 * * 

Mg 44 * * * .53 .64 * * * 1 * * * .43 .67 * .44 * 

Mn -.53 * -.46 * .47 ***** 1 .59 * .70 .54 * .39 * 

Mo -34* * * * * * * * * .59 1 .33 .61 * * * * 

Na -.34 .33 * * -.34 -.51 * * .52 * * .33 1 .54 -.33 .57 -.59 -.43 

Ni -.35 * * * .30 .33 * * * .43 .70 .61 .54 1 * * * * 

Pb * .44 * * .74 * * * -.32 ,67 .54 * -.33 * 1 -.40 .65 .31 

Si * * * * -61 ,40 * * ,52 * * * ,57 * -,40 1 -,66 * 

Sr * * ,61 * .61 * * * * ,44 ,39 * -,59 * ,65 -66 1 ,62 

Ti 31 * * * .46 .59 * 46 * * * * -.43 * .31 * .62 1 

V * * * * * * * * .46 * * -.52 .38 * -.31 * * -.30 

2n * .57 * * * * * * * -.42 .43 * .69 .64 * * * -.34 

Zr 68 -.38 * * .42 -.41 -.70 67 * -42 ,39 * * * -38 ,58 -.36 .59 

OTHER ABYSSAL PLAINS, >3,000 m 

Al 1 * * -0.52 -0,30 * * * 050 * -0.56 -0.30 * * * 065 * * 

Ba *1 * .56* * * * * * * * * * * * * * 

Ca * * 1 * * * * * * 0.30 ******** 

Cd -.52 .56 * 1 -.48 * 0.84 -0,71 -,94 ,99 ,63 ,31 -0,77 0,85 -0,36 * * * 

Co -,30 * * -,48 1 **, 36 ******* -,44 0,48 * 

Cr * * * * * 1 * * * * * * -.34 * * .57 -.35 ♦ 

Cu * * * .84 * * 1 -.53 * * ,58 * * ,82 -,30 * * * 

Fe * * * -.71 .36 * -53 1 -,32 * -,36 * * -.49 .37 * .51 0.30 

K 50 * * -.94 * * * -.32 1 * -.33 * * * * ,55 -31 * 

Mg * * ,30, 99* * * * *1 * * * * * * * * 

Mn -.56 * * .63 * ♦ ,58 -,36 -.33 * 1 .45 * .66 * -.62 * * 

Mo -.30 * * .31 ****** ,45 1 * .36 * -.34 * * 

Na * * * -.77 * -34 ******i ***** 

Ni * * * ,85 * * .82 -.49 * * .66 .36 * 1 * -.30 * * 

Pb * * * -.36 * * -.30 .37 ****** 1 * ,31 * 

Si 65 * * * -,44 ,57 * * ,55 * -.62 -.34 * -.30 * 1 -.35 * 

Sr * * * * .48 -.35 * ,51 -31 ***** ,31 -.35 1 .43 

Ti * * * * * * * .30 ******** .43 1 

V * * * * * * * .38 * * * .36 * * * -.42 * * 

Zn -.32 ***** .32 ♦ * * .30 * * .33 * * * * 

Zr * * * * * -.33 * .42 ******* -.34 * * 

OTHER SEAMOUNTS, <3,000 m 

Al 1 * -0.39 * * -0.33 * * * * -0.30 * * * * 0.59 -0,47 * 

Ba * 1 * 0,98 * * * -0,52 * 0,42 ,53 * * * * -,34 ,31 -0,36 

Ca -,39 ♦ 1 .74 * * ♦ -.40 -0.33 * * * -0,46 * * -,46 ,63 -,40 

Cd * .98 ,74 1 -0.37 -,99 0.54 * * * -.44 * * 0,49 -0,34 * * * 

Co * * * -.37 1 * * * ** * * * .30 .67 -.35 * .60 

Cr -.33 * * -.99 * 1 * .54 .31 * * * -.40 * * * * -.35 

Cu * * * .54 * * 1 * * .40 * * * .44 * * * * 

Fe * -.52 -.40 * * .54 * 1 * * -.30 ****** .39 

K * * -.33 **.31**1 ******* -.30 * 

Mg * .42 * * * * .40 * * 1 * * -.45 .34 * * -.37 * 

Mn -.30 .53 * -.44 * * * -.30 * * 1 * .34 .38 ♦ * * * 

Mo * * * * * * * * * * *1 .61 * .31 * * * 

Na * * -.46 * * -.40 * * * -.45 .34 .61 1 ***** 

Ni * * * .49 .30 * .44 * * .34 .38 * * 1 * * * * 

Pb * * * -.34 .67 ***** * 0.31 * * 1 * * .36 

Si 59 -.34 -.46 * -.35 **********1 -.55 * 

Sr -.47 .31 .63 * * * * * -.30 -.37 ***** -.55 1 * 

Ti * -.36 -.40 * .60 -.35 * .39 ****** .36 * * 1 

V 46 -.50 -.53 * * * .34 .42 .32 ******* * .30 

Zn * * * .30 * * .40 * * * * * -.45 .48 * * * * 

Zr 52 ****** .30 ********** 

* No significant correlation found. Coefficients <-0.3 or >0.3 are considered significant. 



Zn 









* 


* 


0.68 


* 


0.57 


-.38 


* 


* 


■k 


* 


* 


•k 


* 


* 


.42 


* 


* 


-41 


* 


* 


-,70 


* 


* 


.67 


0.46 


* 


* 


* 


-.42 


-.42 


* 


,43 


,39 


-.52 


* 


* 


.38 


,69 


* 


* 


,64 


* 


-.31 


* 


-.38 


* 


* 


.58 


* 


* 


-.36 


-.30 


-,34- 


.59 


1 


,31 


* 


.31 


1 


-.59 


* 


-.59 


1 



* -0.32 



.32 



0.38 



.36 



-.42 



-0.33 

* 

.42 



.30 



.33 



-.34 



0.46 


* 


-.50 


* 


-.53 


* 


* 


0.30 


* 


* 


* 


* 


.34 


.40 


.42 


* 


.32 


* 


* 


* 


* 


* 


* 


* 


* 


-.45 


* 


.48 



0.52 



.30 



.30 



Table 20 gives the elemental variation by sampling site for 
the nodule in figure 61 . Figures 62 through 65 show spatial 
distribution with respect to discrete sample locations on the 
same nodule for the elements Cu and Ni, Co and Zn, Fe and 
Pb, and Ba and Ce. Analysis of the sample sites was 
performed by neutron activitation analysis and atomic 
absorption spectrophotometry using small samples from 
each site. 

Figures 62 through 65 show that concentrations of Cu vary 
directly with Ni and Zn and inversely with Ce, Fe, and Pb. 



Barium does not appear to snow any relationship and could 
be considered as associated with the accessory mineral 
phase. These plots show the tendency of Cu, Ni, Zn, and 
possibly Co in this nodule section to be associated with the 
Mn phase and Ce and Pb to be associated with the Fe phase. 
Although not shown, Mn varies similarly with the Cu and Ni 
scans (see table 20). Figure 61 also shows the amount of 
layering that takes place during nodule growth and the 
differences in light and dark areas. 



55 



♦*•*!%►, 



f^1*sr. 




Scale, cm 



Figure 61. — Unpolished cross section of nodule DH 9-9 (location 21°45' N., 113°10'W, 3,500-m water 
depth). Numbered circles indicate locations of 24 discrete sampling sites for analysis. 



Table 20. — Nodule cross section sample locations and analysis, figure 61 



Sample Weight-percent 

location Ba ^^ ^u Fe Mn 

1 0.251 0.05 0.45 7.8 23.5 

2 212 .02 .61 4.6 27.5 

3 232 .03 .55 5.3 25.5 

4 285 .06 .51 7.4 25.0 

5 335 .06 .56 7.7 24.5 

6 445 .04 .67 4.5 28.5 

7 504 .03 .70 3.4 29.5 

Sand 17 637 .13 .51 9.6 24.0 

9 ND ND .53 ND 25.0 

10 and 15 774 .18 .53 7.7 27.5 

11 and 12 ND .16 .66 9.6 26.5 

13and14 1.270 .10 .67 5.6 28.5 

16 583 .14 .50 12.1 21.5 

18 ND .10 .58 6.4 26.0 

19 511 .05 .73 4.8 27.5 

20 317 .04 .74 5.3 27.5 

21 303 .04 .65 5.9 26.5 

22 282 .06 .63 6.1 26.0 

23 292 .04 .49 5.8 26.5 

24 265 .04 .40 6.2 26.5 

ND Not detected. ' Insoluble in HCI. 



Ni 



Pb Zn 



Parts per million 



Ce 



Cr Cs Eu 



Hf 



La 



Lu Sc Sm Ta Tb 



Th Yb ^'■P'^' 



0.85 

1.00 

.92 

.82 

.80 

.80 
.76 
.74 
.78 
.98 

.93 
1.09 
.60 
.64 
.92 

1.04 
.94 
.96 
.80 
.80 



0.04 0.31 
.02 .34 



.02 
.03 
.02 

.02 
.01 
.03 
.04 
.02 

.03 
.02 
.02 
.02 
.02 

.02 
,02 
.04 
.02 
.02 



.30 
.27 
.25 

.36 
.43 
.18 
.18 
.18 

.20 
.21 
.15 
.16 
.30 

.33 
.36 
.33 
.34 
.34 



203 
115 
146 
199 

215 

126 
86.8 
252 

ND 
215 

ND 
216 
185 
190 
109 

144 
130 
196 
161 
170 



29.3 
19.9 
21.3 
22.2 
19.7 

16.9 
22.3 
30.1 
ND 
32.5 

ND 
14.9 
33.8 
29.3 
20.9 

24.9 
18.5 
22.2 
24.1 
22.9 



24.5 
30.1 
29.5 
293 
31.8 

40,8 
15.1 
25.8 
ND 
23.7 

20.2 
21.4 
22.0 
32.6 
30.3 

35.0 
30.1 
24,5 
26,4 
24,2 



7,1 
5,0 
5,6 
7,1 
6,6 

5,2 
4,6 
4,4 
ND 
4,4 

5,6 
3,8 
3,8 
3,8 

4,5 

4,5 
5,5 
6,1 
5,9 
6,1 



4,2 147 2,8 

2,8 87,4 1.8 

ND 96.1 1.9 

ND 132 

ND 136 



2.7 
2.7 



2.1 
1.8 
2.2 



2.9 104 

3.0 111 

7.3 143 

ND ND ND 

2.9 115 1.7 

9.2 ND ND 

ND 121 1.6 

6.9 111 2.0 

2.8 104 1.6 

ND 105 1.9 

4.8 101 1.9 

2.7 112 2.3 

ND 126 2,6 

3.7 117 2,5 

3.8 114 2,4 



4,5 38,7 

3,3 20,6 

3.1 23.3 

3.9 29.5 

4.5 28.2 

2.1 24.3 

2.6 22.0 
7.0 25.2 
ND ND 
5.8 20.2 

7.3 ND 
5.0 22.3 

9.7 21.5 

5.2 18.6 
4.5 22.9 

5.2 21.5 

5.0 27.3 

5.4 33.5 

5.1 28.3 

5.5 27.8 



ND 5.2 

1.1 3.7 
1.6 4.1 

2.2 5.0 

1.4 4.6 



.6 
1.2 



3.7 

3.3 

.8 3.4 

ND ND 

3.1 2.0 



2.5 
1.2 
3.8 
1.1 
ND 

.6 
1.4 
ND 
1.4 

.9 



1.0 
1.3 
2.4 
2.3 
3.1 

2.6 
3.4 
3.7 
3.7 
4.1 



24.8 
10.0 
13.2 
20.7 
27.0 

10.4 
7.1 

29.5 
ND 

38.1 

39.1 
16.9 
34.8 
22.3 
11.9 

14.5 
16.3 
19.5 
15.3 
19.1 



18.8 16.0 

12.0 17.7 

13.4 12.7 

18.6 8.4 

18.3 14.2 



13.2 
11.2 



7.8 
7.8 



14.7 13.0 

ND 11.7 

13.7 8.0 

ND 15.0 

11.8 10.4 
14.2 22.1 

10.9 12.3 
13.6 8.0 

13.2 15.4 

15.9 10.0 

18.0 13.5 

18.5 8.7 

16.5 14.4 



56 



1.3 
1.2 
1.1 
1.0 

a. 

-1 .8- 

UJ 

I .' 

.6 
.5 



- 


I I 


1 1 


- 


A 


- 


■A 


/ 


\ IV 


" 


^"Vy 


\ A / ''"^ 


- ^ 

/ 

- / 


Nickel 






Copper 

1 1 


1 1 



1.3 
1.2 
1.1 
1.0 

.8 of 

.7 S 

u 
.6 

.5 

.4 



10 15 

SAMPLE LOCATION 



20 



25 



Figure 62. — Spatial distribution off mcicei and 
copper concentrations witli respect to discrete 
sample locations on nodule cross section DH 9-9, 
figure 61 . 



11.0 



9.0 



7.0 



3.0 



- 


1 




1 




1 






1 




y 










r 










: 












\ 






- 


■i 




\ 




■*'' 


J 


^'^>, 




/ 1 


V,- 




kv \ 


* 

V 


' / » 


V- 


-A 


/\ 




'- 


\ 


- 


\ 


\ 


■i / 




V 




\^ 


/ 




- 






1 Iron 
/ Lead 








\ 


VJ 






1 


\ 


■ 1 




1 






1 





5 10 15 20 

SAMPLE LOCATION 



0.06 



OS 



.04 B 

a 

d 

2 

.03 -* 

.02 t 



Figure 64. — Spatial distribution of iron and lead 
concentrations with respect to discrete sample 
locations on nodule cross section DH 9-9, figure 
61. 



0.20 



0.6 




10 15 

SAMPLE LOCATION 



Figure 63. — Spatial distribution off cobalt and 
zinc concentrations with respect to discrete 
sample locations on nodule cross section DH 9<9, 
ffigure 61 . 



1.6 



5 1.2 




10 15 

SAMPLE LOCATION 



280 



240 



200 



- 120 



Figure 65. — Spatial distribution of barium and 
cerium concentrations with respect to discrete 
sample locations on nodule cross section DH 9-9, 
figure 61. 



57 



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97. Monget, J. M., J. W. Murray, and J. Mascle. A World-Wide 
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98. Murata, K. J., and R. C. Erd. Composition of Sediments From 
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99. Murray, J. W. Iron Oxides. Ch. in Marine Minerals, ed. by R. 
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100. Murray, J. W., and J. G. Dillard. The Oxidation of Cobalt (II) 
Adsorbed on Manganese Dioxide. Geochim. Cosmochim. Acta, v. 
43, 1979, pp. 781-787. 

101. Murray, J., and A. F. Renard. Deep-Sea Deposits. Rept. on 
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Years 1873-1876, Longmans and Co., London, England. 

102. Nakanishi, T., M. Oohashi, M. Higashi, and M. Sakanove. 



59 



Radiochemical Studies of Deep-Sea Manganese Nodules. Sci. Rept. 
Kanazawa Univ., Kanazawa, Japan, v. 22, No. 1, June 1977, pp. 
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103. Nohara, M. Manganese Minerals in Ferromanganese 
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104. Okada, A., T. Minakuchi, and M. Shima. Study on the 
Manganese Nodule (V). Thermal Studies of the Iron-Manganese 
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105. Okada, A., and M. Shima. Study on the Manganese Nodule. 
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106. Ostwald, J., and F. W. Frazer. Chemical and Mineraloglcal 
Investigations on Deep Sea Manganese Nodules From the Southern 
Ocean. Miner. Deposita, v. 8, 1973, pp. 303-311. 

107. Piper, D. Z., and M. Williamson. Composition of Pacific 
Ocean Ferromanganese Nodules. Marine Geol., v. 23, 1977, pp. 
285-303. 

108. Price, N. B., and S. E. Calvert. Compositional Vairation in 
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109. Rancltelli, L. A., and R. W. Perkins. Major and Minor 
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110. Riley, J. P., and P. SInhaseni. Chemical Composition of 
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111. Schweisfurth, R. Manganknollen im Meer. Naturwissens- 
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60 



APPENDIX.— GLOSSARY OF MINERALOGICAL TERMS 



Accrete. — The increase in size of an inorganic material by 
the external addition of fresh particles, as by adhesion. 

Acicular. — A crystal that is needlelike in form. 

Amorphous. — A mineral that lacks crystalline structure, or 
whose internal arrangement is so irregular that there is no 
characteristic external form. 

Angstrom (A). — A unit of length, used to express the length 
of light waves, equal to 10-^ micrometer or 10° centimeter. 

Antiferromagnetic. — A type of magnetic order in which the 
moments of neighboring magnetic ions are alined antipara- 
llel, so that there is no macroscopic spontaneous magnetiza- 
tion. 

Antithetic. — Concentration of elements in rocks or minerals 
that vary inversely from one to the other. 

Authigenic. — Rock constituents and minerals formed or 
generated in place, not having been transported but derived 
locally on the spot where they are now found. 

6af/7ymefr/c.— Concerning the depth and topography of 
the ocean floor. 

Benthic. — Pertaining to the ocean bottom, including 
marine life found there. 

Botryoidal. — Having the form of a bunch of grapes. 

Calcareous. — A material that contains a substantial 
amount of calcium carbonate. 

Cell parameters. — The length of axes in the unit cell, given 
in angstroms. 

elastics. — Rocks or sediments composed principally of 
broken fragments that are derived from preexisting rocks or 
minerals and that have been transported individually for 
some distance from their places of origin. 

Colloidal. — Fine-grained matter in suspension in seawater 
that does not occur in crystalline form. Smaller than clay 
particles. 

Cryptocrystalline. — Crystalline substances of such fine- 
grained aggregates that their crystalline nature cannot be 
determined by an optical microscope, but can be determined 
by X-ray diffraction. 

Crystal lattice. — The three-dimensional, regularly repeat- 
ing atomic arrangement of a crystal, each point of which has 
identical surroundings. The lattice is built by the regular, 
parallel translation in space of the unit cell. 

Detrital. — Loose rocks or minerals that are worn off or 
removed by mechanical means, as by disintegration or 
abrasion, later forming other rocks, minerals, or sediments. 

Diagenesis. — The recombination or rearrangement of a 
mineral resulting in a new mineral. 

d-spacing. — In refraction of X-rays by a crystal, the 
distance or separation between the successive and identical 
parallel planes in the crystal lattice. 

Epitaxial. — An orientation of a crystal with that of the 
crystalline substrate on which it grew. 

Euhedral. — A crystalline solid with well-formed faces. 

Ferrimagnetic. — A type of magnetic order, magnetic ions 
at different crystal sites are opposed. However, there is a net 
magnetization because of inequality in the number or 
magnitude of atomic magnetic moments at the two sites. 

Hexagonal. — One of the six crystal systems, having four 
crystallographic axes, three of which are of equal length, and 



are horizontal and intersect at angles of 1 20°. The fourth axis 
(vertical) is of different length and perpendicular to the plane 
of the other three. 

Interstices. — Openings or spacings between objects. 

Isometric. — One of the six crystal systems, having three 
mutually perpendicular axes of equal lengths. 

Isostructural. — Minerals related to each other by analo- 
gous structures, generally having a common anion, and 
displaying extensive ionic substitution. 

Isotropic. — A crystal whose physical properties do not vary 
according to crystallographic direction. Crystals that belong 
to the isometric system. 

Mammillary. — An aggregate of crystals taking the form of 
rounded masses. 

Metastable. — A phase that is stable with respect to small 
disturbances but that is capable of reaction with evolution of 
energy if sufficiently disturbed. 

Monoclinic. — One of the six crystal systems, having three 
unequal axes, two of which are inclined to each other at an 
oblique angle and the third perpendicular to the plane of the 
other two. 

Octahedra. — An atomic structure or arrangement in which 
an ion is surrounded by six ions of opposite charge, whose 
centers form the corners of an octahedron, which is an 
isometric crystal form of eight faces, and which are 
equilateral triangles. 

Orthorhombic. — One of the six crystal systems, having 
three mutually perpendicular axes all of different lengths. 

Polymorph. — A chemical substance that can crystallize in 
more than one form, such as rhombic and monoclinic sulfur. 

Psilomelane. — A general term for mixtures of manganese 
minerals. 

Rhombohedral. — A crystal form that is a parallelepiped 
whose six identical faces are rhombs; that is, oblique, 
equilateral parallelograms. Characteristic of the hexagonal 
system. 

Siliceous. — An abundance of free silica. 

Solid solution. — A single crystalline phase that may vary in 
composition within finite limits without the appearance of an 
additional phase. 

Space group. — In a crystal s*r;jcture, one of 230 different 
ways of arranging atoms in a homogeneous array. 

Supergene. — A mineral deposit or enrichment formed by 
descending solutions. 

Tetragonal. — One of the six crystal systems, having three 
mutually perpendicular axes, two of which (the horizontal 
axes) are of equal length, but the vertical axis is shorter or 
longer than the other two. 

Triclinic. — One of the six crystal systems, having a onefold 
axis of symmetry and three axes of unequal lengths that all 
intersect at oblique angles. 

Unit cell. — The fundamental parallelepiped that forms a 
crystal lattice by regular repetition in space. 

Zeolite. — Signifies a group of hydrous aluminosilicates that 
are analogous in composition to the feldspars. They are 
characterized by their easy and reversible loss of water of 
hydration, and their swelling up on heating. 



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